Search

CN-121978074-A - Visible/ultraviolet double-light synergistic enhancement substrate, preparation method thereof and application thereof in veterinary drug rapid detection

CN121978074ACN 121978074 ACN121978074 ACN 121978074ACN-121978074-A

Abstract

The invention discloses a visible/ultraviolet double-light synergistic enhancement substrate, a preparation method thereof and application thereof in veterinary drug rapid detection. The method adopts a gas-liquid interface self-assembly technology and a photo-welding process to prepare the heterojunction composite Raman substrate Bi of the Bi-doped zinc oxide nano array and the sea urchin-shaped silver nano particles, namely ZnO-SUSNs. The Bi-SUSNs composite Raman substrate has excellent visible light/ultraviolet light dual response characteristics, and can greatly improve the detection sensitivity of target molecules under double-light driving by utilizing a PIERS mechanism. The method can realize trace detection of veterinary drugs such as malachite green, crystal violet and furacilin without complex pretreatment. In addition, the composite substrate also has the function of photocatalytic degradation, can realize self-cleaning and recycling, and has the advantages of low preparation cost, high detection speed, good repeatability and the like.

Inventors

  • JIANG XIAOHONG
  • LIU GUOWEI
  • CAI CHAOYU

Assignees

  • 南京理工大学

Dates

Publication Date
20260505
Application Date
20260115

Claims (10)

  1. 1. The preparation method of the visible/ultraviolet double-light synergistic enhancement substrate is characterized by comprising the following steps of: (1) Adopting a three-electrode system, taking a conductive substrate as a working electrode, taking a mixed aqueous solution of zinc nitrate and bismuth nitrate as an electrolyte, adopting a two-step electrochemical deposition method, firstly applying constant potential deposition in a high-temperature water bath at 65-85 ℃ to prepare a seed layer, then adding hexamethylenetetramine into the electrolyte, applying constant current deposition in the high-temperature water bath at 65-85 ℃ to prepare a nano rod array, and washing and drying after the reaction is finished to obtain Bi ZnONRAs; (2) Dropwise adding ethanol dispersion liquid of sea urchin-shaped silver nano particles onto the surface of a silver nitrate solution, forming a SUSNs self-assembled film by utilizing a gas-liquid interface self-assembly technology, transferring the SUSNs self-assembled film to the surface of Bi ZnONRAs by a dipping and pulling method, performing in-situ photo-welding under ultraviolet irradiation, taking out, washing and drying to obtain the Bi ZnO-SUSNs composite Raman substrate.
  2. 2. The method of claim 1, wherein in step (1), the conductive substrate is ITO glass.
  3. 3. The preparation method according to claim 1, wherein in the step (1), the constant potential deposition time is 50 s-120 s, the constant potential is-0.5 to-2V, the constant current deposition time is 3600 s-7200 s, and the constant current is-1 mA to-1.5 mA.
  4. 4. The method according to claim 1, wherein in the step (2), the concentration of the ethanol dispersion of the sea urchin-shaped silver nanoparticles is 0.1 to 0.5 mg/ml, and the concentration of the silver nitrate solution is 8 to 15 mM.
  5. 5. The method according to claim 1, wherein in the step (2), the ultraviolet irradiation time is 20 to 40 minutes.
  6. 6. The visible/ultraviolet dual light cooperative reinforcement substrate prepared by the preparation method according to any one of claims 1 to 5.
  7. 7. The use of a visible/ultraviolet dual light synergistically enhanced substrate according to claim 6 in SERS or PIERS detection veterinary medicine.
  8. 8. The use according to claim 7, wherein the veterinary drug is selected from more than one of malachite green, crystal violet and furacilin.
  9. 9. The application according to claim 8, wherein the specific application method is: (1) Dripping the to-be-detected liquid on a Bi ZnO-SUSNs composite Raman substrate, directly collecting Raman spectrum, or pre-irradiating under visible light or ultraviolet light to activate defective state charge transfer, and then collecting Raman spectrum; (2) Comparing the Raman spectrum of the veterinary drug standard with the Raman spectrum signal of the liquid to be tested, and performing qualitative analysis on the veterinary drug type in the liquid to be tested; (3) And substituting the Raman spectrum signal of the liquid to be detected into the linear relation between the veterinary drug concentration and the Raman spectrum signal, and quantifying the veterinary drug concentration in the liquid to be detected.
  10. 10. The use according to claim 9, wherein in step (1), the pre-irradiation time under visible light is 10 to 15min and the pre-irradiation time under ultraviolet light is 25 to 30min.

Description

Visible/ultraviolet double-light synergistic enhancement substrate, preparation method thereof and application thereof in veterinary drug rapid detection Technical Field The invention belongs to the technical field of rapid detection of food safety, and particularly relates to a visible/ultraviolet double-light synergistic enhancement substrate, a preparation method thereof and application thereof in veterinary drug rapid detection. Background Malachite green, crystal violet and nitrofurans (e.g., furacilin) have been widely used in aquaculture to prevent fish saprolegniasis and bacterial infection. Because the residual concentration of the medicines in the aquatic product matrix is extremely low and the components are complex, it is very necessary to develop a rapid, sensitive and anti-interference quantitative detection method for guaranteeing the food safety. Surface Enhanced Raman Scattering (SERS) technology has become a powerful tool for trace species detection by virtue of its fingerprint recognition capability and single molecule level detection sensitivity. Conventional SERS relies mainly on electromagnetic field enhancement （EM）（Xu, H., Aizpurua, J., Käll, M., Apell, P., 2000. Electromagnetic contributions to single-molecule sensitivity in surface-enhanced Raman scattering. Phys. Rev. E 62, 4318-4324. https://doi.org/10.1103/PhysRevE.62.4318）. of noble metal nanostructures (e.g., gold, silver) to further enhance sensitivity, photo-enhanced raman spectroscopy (PIERS) techniques have been proposed. The technique introduces a semiconductor material that generates charge transfer under illumination, thereby further enhancing the signal by Chemical Mechanism (CM) （Panariello, L., Chuen To, K., Khan, Z., et al, 2021. Kinetics-based design of a flow platform for highly reproducible on demand synthesis of gold nanoparticles with controlled size between 50 and 150 nm and their application in SERS and PIERS sensing. Chemical Engineering Journal 423, 129069. https://doi.org/10.1016/j.cej.2021.129069）. However, the conventional SERS and PIERS technologies have significant challenges and limitations in practical aquatic product detection (1) fluorescence background interference, namely, a common wide band gap semiconductor (such as pure ZnO) generally only responds to ultraviolet light, and ultraviolet light excitation can cause strong fluorescence background of biological samples (such as fish meat extract), so that the signal to noise ratio is seriously reduced, and detection accuracy is affected. (2) Signal uniformity and stability the traditional SERS substrate is prepared by a dripping method, a coffee ring effect exists, the signal uniformity is poor, and the noble metal particles which are physically adsorbed are easy to fall off, so that the reusability of the substrate is limited. (3) The structural analogues are difficult to distinguish, malachite green and crystal violet belong to triphenylmethane substances with highly similar structures, and can be difficult to accurately distinguish by naked eyes or conventional spectral analysis. In the prior art, bi-doped zinc oxide (Bi-ZnO) is mostly used in the fields of photocatalytic degradation (such as dyes and antibiotics), VOCs gas sensing and antibiosis. Although studies have demonstrated that Bi doping narrows the energy band and increases the surface oxygen vacancies, thereby enhancing the photoresponse and charge transfer efficiency, these properties are currently mainly served for the enhancement （Kazmi, J., Ooi, P.C., Goh, B.T., wt al, 2020. Bi-doping improves the magnetic properties of zinc oxide nanowires. RSC Adv. 10, 23297-23311. https://doi.org/10.1039/D0 RA03816 D) . of catalytic and sensing properties, and no report has been made on the use of it in the construction of PIERS substrates, particularly in the application of it in rapid screening of forbidden veterinary drugs in aquatic products. Disclosure of Invention The invention aims to provide a visible/ultraviolet double-light synergistic enhancement substrate, a preparation method thereof and application thereof in veterinary drug rapid detection. The invention constructs a Bi-doped ZnO nanorod array combined sea urchin-shaped silver nanoparticle composite substrate (Bi: znO-SUSNs), realizes visible light response by utilizing defect energy levels introduced by Bi doping, avoids fluorescence interference, realizes uniform and firm load by gas-liquid interface self-assembly and photo-welding, and realizes ultrasensitive detection and qualitative and quantitative analysis of various veterinary drugs in a complex substrate by utilizing double photoinduced enhanced Raman effects of a doped semiconductor and a noble metal composite substrate. The technical scheme for realizing the purpose of the invention is as follows: The preparation method of the visible/ultraviolet double-light synergistic enhancement substrate comprises the following steps: (1) Adopting a three-electrode system, taking