CN-122016754-A - Mass spectrum Raman combination substrate and preparation method thereof

CN122016754ACN 122016754 ACN122016754 ACN 122016754ACN-122016754-A

Abstract

The application discloses a mass spectrum Raman combined substrate and a preparation method thereof, relates to the technical field of analysis and detection, and can provide a dual-function substrate which can simultaneously support electrospray mass spectrum detection and surface enhanced Raman detection, is mutually noninterfere and is suitable for on-site rapid operation. The substrate comprises a substrate film and at least one directional liquid transmission channel positioned on the surface of the substrate film, wherein a Raman detection area and a mass spectrum detection area are arranged in the channel, the mass spectrum detection area is arranged at the tail end of the channel, the tail end is of a pointed structure, the substrate film at the tail end comprises a metal conducting layer, the Raman detection area is arranged at any position in the channel which is not overlapped with the mass spectrum detection area, the substrate film of the Raman detection area is provided with a metal nano structure for realizing surface enhanced Raman detection, the Raman detection device carries out Raman detection on a liquid sample after the liquid sample flows through the Raman detection area, and when the liquid sample flows to the mass spectrum detection area, the mass spectrum detection device carries out mass spectrum detection on the liquid sample.

Inventors

HUO XINMING
LIN JINGXIONG
ZHOU JIANHUA
LEI SHUO

Assignees

中山大学·深圳
中山大学

Dates

Publication Date: 20260512
Application Date: 20260205

Claims (10)

1. The mass spectrometry Raman combined substrate is characterized by comprising a substrate film and at least one directional liquid transmission channel positioned on the surface of the substrate film, wherein a Raman detection area and a mass spectrometry detection area are arranged in the directional liquid transmission channel, and the directional liquid transmission channel is used for guiding a liquid sample to be detected to realize directional migration; the mass spectrum detection area is arranged at the tail end of the directional liquid transmission channel, the tail end of the directional liquid transmission channel corresponding to the mass spectrum detection area is of a pointed structure, and the substrate film at the tail end of the directional liquid transmission channel comprises a metal conductive layer; The Raman detection area is arranged at any position which is not overlapped with the mass spectrum detection area in the directional liquid transmission channel, and a metal nano structure is arranged on a substrate film corresponding to the Raman detection area and is used for realizing surface enhanced Raman detection; The liquid sample realizes directional migration in the directional liquid transmission channel, after flowing through the Raman detection area, the Raman detection device performs Raman detection on the liquid sample in the Raman detection area, and when flowing to the mass spectrum detection area, the mass spectrum detection device performs mass spectrum detection on the liquid sample.
2. The substrate of claim 1, wherein the raman detection area and the mass spectrometry detection area are disposed in the same directional liquid transport channel, or wherein the raman detection area and the mass spectrometry detection area are disposed in different directional liquid transport channels, respectively.
3. The substrate of claim 1, wherein the directional liquid transport channels comprise any one or more of a channel structure channel, a periodic asymmetric ridge-valley structure channel, and a surface wettability gradient structure channel.
4. The substrate of claim 1, wherein the raman detection area is 0.05-100mm2; the metal nano structure is prepared from gold and/or silver, or is prepared from a core-shell structure, a multilayer structure or a composite structure formed by gold and silver; The morphology of the metal nano structure comprises a metal nano film structure, a nano island structure, a nano particle stacking structure, a nano columnar structure and a periodic array structure; the thickness of the metal nano structure ranges from 2nm to 200nm.
5. The substrate of claim 1, wherein the tipped structure is formed by tipped an end of any one of the directional liquid transfer channels, the tipped processing being capable of forming a single-tipped, double-tipped or multi-tipped array structure, wherein the tip angle ranges from 5 ° to 70 °; the metal conductive layer is prepared from gold and/or platinum; when the liquid sample flows to the pointed structure at the tail end of the directional liquid transmission channel, electrospray is formed under the action of an external electric field.
6. The substrate of claim 1, wherein the substrate film is made of a polymer material, a glass material, a silicon-based material, a metal material, or a metal composite material.
7. A method for preparing a mass spectrometry raman combination substrate according to any one of claims 1 to 6, comprising: forming at least one directional liquid transmission channel on the surface of the substrate film, wherein the directional liquid transmission channel is used for guiding a liquid sample to be detected to realize directional migration; a Raman detection area and a mass spectrum detection area are arranged in the directional liquid transmission channel, wherein the mass spectrum detection area is arranged at the tail end of the directional liquid transmission channel, and the Raman detection area is arranged at any position which is in the directional liquid transmission channel and does not coincide with the mass spectrum detection area; adopting a first processing mode, processing the tail end of the directional liquid transmission channel corresponding to the mass spectrum detection area into a pointed structure, and forming a metal conductive layer on a substrate film at the tail end of the directional liquid transmission channel; forming a metal nano structure on the substrate film corresponding to the Raman detection area by adopting a second processing mode; The liquid sample realizes directional migration in the directional liquid transmission channel, the Raman detection device carries out Raman detection on the sample in the Raman detection area after the liquid sample flows through the Raman detection area, and the mass spectrum detection device carries out mass spectrum detection on the liquid sample when the liquid sample flows to the mass spectrum detection area.
8. The method of claim 7, wherein forming at least one directional liquid transport channel on the surface of the substrate film comprises: and forming at least one directional liquid transmission channel on the surface of the substrate film by adopting a compression molding, etching, laser processing or photo-curing printing mode.
9. The method of claim 7, wherein the first machining mode comprises laser cutting, physical shaping, micro milling, and chemical etching.
10. The method of claim 7, wherein the second processing mode comprises magnetron sputtering, evaporation, annealing reconstruction, nanoparticle self-assembly, template-assisted deposition, photolithography, and etching.

Description

Mass spectrum Raman combination substrate and preparation method thereof Technical Field The application relates to the technical field of analysis and detection, in particular to a mass spectrum Raman combination substrate and a preparation method thereof. Background Raman spectroscopy and mass spectrometry are commonly used analytical detection techniques because of their ability to provide molecular vibration information and mass to charge ratio information. Because raman spectrum and mass spectrum technology have obvious complementarity in the information dimension, raman spectrum can provide molecular vibration fingerprint for structure screening, and mass spectrum can provide mass-to-charge ratio and fragment information for structure confirmation, therefore, the detection accuracy and reliability of complex samples can be obviously improved by combining the two on the same platform. At present, paper-based materials are generally used as sample carriers when combining paper spray mass spectrometry with Surface Enhanced Raman Scattering (SERS) detection, but the characteristics of uncontrollable liquid absorption, non-uniformity of fiber structures, liquid diffusion and the like of the paper-based materials can lead to random sample migration paths, unstable spraying processes, and large ionization efficiency fluctuation. In addition, paper-based materials are difficult to carry metal nanostructures with precisely controllable morphology, making their enhancement effect limited and their repeatability poor when used as SERS substrates. Furthermore, at present, a spraying area of paper spraying and an SERS detection area cannot be clearly partitioned on the same substrate, so that two detection modes interfere with each other, and a true synergistic dual-mode combination cannot be realized. In summary, there is still a lack of a dual-function substrate capable of supporting electrospray mass spectrometry detection and surface enhanced raman detection simultaneously, and the two are not interfered with each other, which is suitable for on-site rapid operation. Disclosure of Invention The application provides a mass spectrum Raman combined substrate and a preparation method thereof, which can provide a dual-function substrate capable of simultaneously supporting electrospray mass spectrum detection and surface enhanced Raman detection, and the two substrates are mutually noninterfere and are suitable for on-site rapid operation. In order to achieve the above purpose, the application adopts the following technical scheme: According to a first aspect of the embodiment of the application, a mass spectrometry Raman combination substrate is provided, wherein the substrate comprises a substrate film and at least one directional liquid transmission channel positioned on the surface of the substrate film, a Raman detection area and a mass spectrometry detection area are arranged in the directional liquid transmission channel, and the directional liquid transmission channel is used for guiding a liquid sample to be detected to realize directional migration; the mass spectrum detection area is arranged at the tail end of the directional liquid transmission channel, the tail end of the directional liquid transmission channel corresponding to the mass spectrum detection area is of a pointed structure, and the substrate film at the tail end of the directional liquid transmission channel comprises a metal conductive layer; The Raman detection area is arranged at any position which is not overlapped with the mass spectrum detection area in the directional liquid transmission channel, and a metal nano structure is arranged on a substrate film corresponding to the Raman detection area and is used for realizing surface enhanced Raman detection; The liquid sample realizes directional migration in the directional liquid transmission channel, after flowing through the Raman detection area, the Raman detection device performs Raman detection on the liquid sample in the Raman detection area, and when flowing to the mass spectrum detection area, the mass spectrum detection device performs mass spectrum detection on the liquid sample. As one possible implementation, the Raman detection area and the mass spectrum detection area are arranged in the same directional liquid transmission channel, or the Raman detection area and the mass spectrum detection area are respectively arranged in different directional liquid transmission channels. As one possible implementation, the directional liquid transfer channels include any one or more of a channel structure channel, a periodic asymmetric ridge-valley structure channel, and a surface wettability gradient structure channel. As a possible implementation manner, the area of the raman detection area is 0.05-100mm2; the metal nano structure is prepared from gold and/or silver, or is prepared from a core-shell structure, a multilayer structure or a composite structure formed by gold and sil