CN-122016760-A - Dynamic Raman detection device and detection method based on magnetic control cluster

CN122016760ACN 122016760 ACN122016760 ACN 122016760ACN-122016760-A

Abstract

The invention provides a dynamic Raman detection device and method based on a magnetic control cluster, wherein the device comprises a magnetic SERS probe, a magnetic field generating unit for generating a programmable time-varying magnetic field to drive the magnetic SERS probe to form a dynamic micro-nano motor cluster, a Raman detection unit for carrying out laser irradiation on a magnetic control cluster area and collecting Raman scattering signals, an imaging unit for carrying out real-time monitoring and positioning on the magnetic control cluster, and a control unit, wherein a region to be detected is positioned in an effective working space of the magnetic field generating unit, and the control unit is respectively and electrically connected with the magnetic field generating unit, the Raman detection unit and the imaging unit and is used for adjusting magnetic field parameters, synchronously controlling detection time sequence and processing imaging and spectrum data. According to the technical scheme, the dynamic motion characteristic of the micro-nano motor cluster and the surface Raman enhancement effect are combined, the probe is driven by an external magnetic field to form a reconfigurable dynamic cluster, and high-sensitivity and accurate positioning detection in a complex environment is realized.

Inventors

MA XING
JIN DONGDONG
ZHAO DONGFANG
YE ZIMING

Assignees

哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院)

Dates

Publication Date: 20260512
Application Date: 20260302

Claims (7)

1. A dynamic Raman detection device based on a magnetic control cluster is characterized by comprising a magnetic SERS probe, a magnetic field generation unit, a Raman detection unit, an imaging unit and a control unit, wherein the magnetic field generation unit is used for generating a programmable time-varying magnetic field to drive the magnetic SERS probe to form a dynamic micro-nano motor cluster, the Raman detection unit is used for carrying out laser irradiation on a magnetic control cluster area and collecting Raman scattering signals, and the imaging unit is used for carrying out real-time monitoring and positioning on the magnetic control cluster; the magnetic SERS probe has magnetic response characteristics and surface-enhanced Raman scattering activity and is a core-shell structure, an egg yolk-eggshell structure, a Janus structure, a polymer structure or a magnetic microsphere structure with a surface modified with noble metal satellites; The magnetic field generating unit comprises a permanent magnet generating unit, an electromagnetic generating unit or a combination of the permanent magnet generating unit and the electromagnetic generating unit, and can output a rotating magnetic field, an oscillating magnetic field, a superimposed magnetic field or a gradient magnetic field, wherein the permanent magnet generating unit comprises a fixed permanent magnet, a movable mechanical magnetic arm, a rotating magnetic field generator or a Halbach (Halbach) array, the permanent magnet is made of at least one of neodymium iron boron, samarium cobalt or ferrite, and the electromagnetic generating unit comprises at least one of a direct current electromagnet, an alternating current electromagnet, a solenoid, a helmholtz coil, a maxwell coil, a three-dimensional orthogonal coil system or a photoetching plane micro coil; the imaging unit comprises one or more of an ultrasonic imaging unit, an optical imaging unit, an X-ray imaging unit, a computer tomography imaging unit, a magnetic resonance imaging unit, a photoacoustic imaging unit or a thermal imaging unit; the Raman detection unit comprises one of a microscopic confocal Raman spectrometer, an optical fiber Raman spectrometer, a handheld or portable Raman spectrometer, a Fourier transform Raman spectrometer and a custom Raman signal reading module; The control unit is respectively and electrically connected with the magnetic field generation unit, the Raman detection unit and the imaging unit and is used for adjusting magnetic field parameters, synchronously controlling detection time sequence and processing imaging and spectrum data.
2. The dynamic Raman detection device based on the magnetic control cluster according to claim 1, wherein the imaging unit is an ultrasonic imaging unit.
3. The dynamic Raman detection device based on the magnetic control cluster, which is characterized in that the magnetic SERS probe unit comprises a magnetic core, a SERS active component and a protective layer, wherein the magnetic core is one of ferroferric oxide, ferric oxide, pure iron, cobalt and nickel or an alloy thereof or ferrite material, the SERS active component is one of gold, silver, copper, platinum and palladium or an alloy nano material thereof, and the protective layer is a SiO 2 layer with the thickness of 2-5nm and is coated on the surface of the SERS active component.
4. A dynamic Raman detection method based on a magnetic control cluster is characterized by adopting the dynamic Raman detection device based on the magnetic control cluster as set forth in any one of claims 1-3 for detection, and comprising the following steps: Step S1, introducing the magnetic SERS probe into a fluid environment to be detected; S2, generating a programmable time-varying magnetic field through the magnetic field generating unit, and driving the magnetic SERS probes to gather through magnetic dipole interaction to form a dynamic micro-nano motor cluster with a specific geometric shape; S3, adjusting magnetic field parameters through a control unit, maintaining the clusters in a dynamic motion state, enabling high-frequency collision and relative motion to occur between magnetic SERS probes in the clusters, and generating a large number of transient gap hot spots on the basis of steady-state gap hot spots in the flux linkage; And S4, monitoring the cluster position in real time by using an imaging unit, and carrying out laser irradiation on the cluster region and collecting Raman scattering signals by using a Raman detection unit.
5. The method for dynamic Raman detection based on magnetron clusters according to claim 4, wherein in step S2, the magnetic field parameter adjustment of the magnetic field generating unit satisfies any one of the following conditions: when a rotating magnetic field is generated, the magnetic field strength is set to be 4mT, 6mT or 8mT, the rotating frequency is set to be 10-20 Hz, and the magnetic field function is Wherein a R represents the maximum value of the rotating magnetic field strength, ƒ is the frequency of the rotating magnetic field, and B x and B y represent the components of the magnetic field along the x-axis and y-axis, respectively; When an oscillating magnetic field is generated, the magnetic field strength is 15mT, the oscillating frequency is 10Hz, 15Hz or 20Hz, and the magnetic field function is Wherein A O and C O are constants, θ is the angle between the oscillation direction and the y-axis direction, ƒ is the frequency of oscillation, and B x and B y represent the components of the magnetic field along the x-axis and the y-axis, respectively; When a scattering magnetic field is generated, the magnetic field function is that Wherein A xy and A z are the maximum values of the magnetic field strength in the xy plane and the y plane, respectively, ƒ xy and ƒ z are the frequencies of the xy plane rotating magnetic field and the z direction oscillating magnetic field, respectively, and B x 、B y 、B z is the component of the magnetic field along the x-axis y-axis and the z-axis, respectively.
6. The dynamic Raman detection method based on the magnetic control clusters according to claim 4 is characterized in that detection parameters of the Raman detection unit in the step S4 are met, 532nm laser excitation is adopted when crystal violet is detected, laser energy intensity is set to be 5%, single acquisition time is set to be 5 seconds, accumulation times are set to be 2 times, characteristic peaks are set to be 917cm -1 , 633nm laser excitation is adopted when rhodamine 6G is detected, laser energy intensity is set to be 10% and single acquisition time is set to be 10 seconds, accumulation times are set to be 2 times, and characteristic peaks are set to be 613cm -1 .
7. The method of claim 4, wherein the method is used for food safety detection, water quality monitoring, biomedical detection, industrial fluid analysis, microfluidic chip site-directed sampling or micro sample collection and recovery in dangerous environments.

Description

Dynamic Raman detection device and detection method based on magnetic control cluster Technical Field The invention relates to the technical field of Raman detection, in particular to a dynamic Raman detection device and method based on a magnetic control cluster. Background Micro-nano motors (or micro-nano robots) are widely focused on application in the biomedical field due to small size and active motion capability. However, a single micro-nanomotor is small in size and difficult to carry complex functional components. For this reason, controlling the micro-nano motors to form clusters by using external physical fields (such as magnetic fields) to enhance environmental adaptability and functional performance has become a research hotspot. The external physical field (such as a magnetic field) is utilized to control the micro-nano motors to form clusters, so that the environmental adaptability and the functional performance of the micro-nano motors can be enhanced, but the existing magnetic control micro-nano motors are mainly used for drug delivery and less used for dynamic SERS detection. Conventional SERS probes lack active motion capabilities, are difficult to achieve efficient enrichment in complex fluids (e.g., blood), and have problems with difficult localization. Raman spectroscopy is widely used in the field of substance detection and diagnosis due to high sensitivity and high specificity, but still faces many challenges in practical application. On one hand, the traditional Surface Enhanced Raman Scattering (SERS) probes are mostly static probes, signal enhancement is realized only by depending on steady-state hot spots, the sensitivity is insufficient in a complex environment sample, the detection Limit (LOD) is high, the detection requirement of a low-concentration target object is difficult to meet, on the other hand, the traditional probes lack active motion capability and can only flow along with waves, the traditional probes can not reach a specific area in a countercurrent way in a blood vessel or a micro-channel with a flow velocity, and high-efficiency enrichment cannot be realized in the low-concentration sample, and in addition, the Raman probes are difficult to be directly observed and positioned by optical equipment in a non-transparent environment (such as biological tissues and whole blood), so that the problems of 'invisible and inaccurate detection' are caused, and the application of the Raman probes in the detection of living body deep tissues is severely limited. Therefore, developing a raman detection technology capable of solving the problems of insufficient signal enhancement, lack of active addressing capability and difficulty in deep positioning is a technical problem to be solved in the field. Disclosure of Invention Aiming at the technical problems, the invention discloses a dynamic Raman detection device and a detection method based on a magnetic control cluster, which are used for forming a reconfigurable dynamic cluster by combining the dynamic motion characteristic and the surface Raman enhancement effect of a micro-nano motor cluster and utilizing an external magnetic field to drive a probe, so that the problems of insufficient signal enhancement, incapability of active addressing and difficult deep detection and positioning in the existing Raman detection technology are solved, and the high-sensitivity and accurate positioning detection under a complex environment is realized. In this regard, the invention adopts the following technical scheme: A dynamic Raman detection device based on a magnetic control cluster comprises a magnetic SERS probe, a magnetic field generation unit, a Raman detection unit, an imaging unit and a control unit, wherein the magnetic field generation unit is used for generating a programmable time-varying magnetic field to drive the magnetic SERS probe to form a dynamic micro-nano motor cluster, the Raman detection unit is used for carrying out laser irradiation on a magnetic control cluster area and collecting Raman scattering signals, the imaging unit is used for carrying out real-time monitoring and positioning on the magnetic control cluster, and the area to be detected is positioned in an effective working space of the magnetic field generation unit; the magnetic SERS probe has magnetic response characteristics and surface-enhanced Raman scattering activity and is a core-shell structure, an egg yolk-eggshell structure, a Janus structure, a polymer structure or a magnetic microsphere structure with a surface modified with noble metal satellites; The magnetic field generating unit comprises a permanent magnet generating unit, an electromagnetic generating unit or a combination of the permanent magnet generating unit and the electromagnetic generating unit, and can output a rotating magnetic field, an oscillating magnetic field, a superimposed magnetic field or a gradient magnetic field, wherein the permanent magnet generating unit compri