CN113252637B - Fluorescence background suppression system and suppression method in Raman spectrum detection - Google Patents
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Abstract
The invention relates to a fluorescence background suppression system and a suppression method in Raman spectrum detection. The suppression system comprises a Raman laser and a coded aperture fiber Raman spectrum analysis module; the excitation light output end of the Raman laser is connected with an excitation optical fiber, and an excitation optical fiber collimating lens, an excitation optical fiber coupling lens and a narrow-band optical filter are sequentially arranged in a transmission light path of the excitation optical fiber; the signal input end of the coded aperture fiber Raman spectrum analysis module is connected with a coded aperture fiber array, the coded aperture fiber array is externally connected with a collection fiber, and a collection fiber collimating mirror, a collection fiber coupling mirror and a high-pass Raman filter are sequentially arranged in a transmission light path of the collection fiber; the excitation optical fiber and the collection optical fiber are converged into a bundle at the free end and then integrated into a Raman signal excitation/collection optical fiber probe; the excitation optical fibers in the Raman signal excitation/collection optical fiber probe are positioned at the axis position, and the collection optical fibers are densely distributed by taking the excitation optical fibers as the center.
Description
Technical Field
The invention relates to a spectrum detection technology, in particular to a fluorescence background suppression system and a suppression method in Raman spectrum detection.
Background
The Raman spectrum technology has the advantages of non-contact, no damage, rapidness, accuracy and the like, has great application value in the aspects of pure qualitative analysis, high-precision quantitative analysis, determination of molecular structures and the like, and has application range in various fields of chemistry, physics, biology, materials, medicine, cultural relics, precious stones and the like. However, the intensity of raman scattered light is weak, which is an inherent disadvantage. In general, the intensity of the raman scattered light is about 10 of the intensity of the incident light-10In raman spectroscopy, when a biological tissue sample is irradiated with laser light, not only raman scattered light but also fluorescence is excited, which interferes with the resolution of the raman spectrum. Especially in the Raman spectrum test of the biological tissue, the inhibition effect on the background fluorescence is good and bad, and the analysis and judgment result of the biological tissue component can be directly influenced.
Scholars at home and abroad propose various methods and technologies for inhibiting fluorescence, such as a time domain inhibition method, a high-frequency modulation inhibition method, a frequency shift excitation differential Raman spectrum, a fluorescence background removal method in spectrum post-processing and the like. The occurrence of raman scattered light occurs temporally following excitation light, and the emission of fluorescence is delayed on a time scale from the raman scattered light. The time domain inhibition method utilizes a Kerr gate control or a time gating detector such as a photomultiplier tube, an enhanced CCD camera or a Single Photon Avalanche Detector (SPAD) to realize the inhibition of fluorescent background light. The high-frequency modulation inhibition method inhibits the influence of the fluorescence background by modulating the high frequency of the exciting light and demodulating the Raman spectrum signal according to the difference of Raman scattering and fluorescence responses to high-frequency signals. In a relatively small range, the distribution characteristics of the fluorescence spectrum hardly change greatly with the change in the frequency of the excitation wave, and the raman spectrum shows a shift in the raman spectrum displayed in wavelength closely following the change in the frequency of the excitation wave. Thus, subtraction of spectra obtained from different excitation frequencies can effectively subtract substantially the same fluorescent background, and such techniques include frequency-shifted excitation differential raman spectroscopy (SERDS), Wavelength Modulated Raman Spectroscopy (WMRS), and differential raman spectroscopy (SSRS). The frequency shift excitation differential raman spectroscopy is excited by excitation light with two similar wavelengths, and the wavelength modulation raman spectroscopy adopts a continuously modulated excitation wavelength and a multi-channel lock detector, both of which require more than two excitation light sources with different frequencies. Bell in 1998 firstly proposes an SSRS method, which adopts a grating with a micro-rotatable position, obtains a difference spectrogram of a spectrum before and after micro-rotation of a front grating by utilizing the fine change of a detected spectrum on a detection unit space, and achieves the purpose of inhibiting the fluorescence background by a difference method. The method has the greatest advantages that other optical elements are not additionally arranged, the system is simple and convenient, but the method is realized by two times of measurement.
Disclosure of Invention
The invention aims to provide a fluorescence background suppression system and a fluorescence background suppression method in Raman spectrum detection, and aims to solve the problem that the accuracy of an analysis result is reduced due to a fluorescence background in the conventional Raman spectrum detection.
The purpose of the invention is realized as follows: a fluorescence background suppression system in Raman spectrum detection comprises a Raman laser and a coded aperture fiber Raman spectrum analysis module; the excitation light output end of the Raman laser is connected with an excitation optical fiber, and an excitation optical fiber collimating lens, an excitation optical fiber coupling lens and a narrow-band optical filter are sequentially arranged in a transmission light path of the excitation optical fiber; the signal input end of the coded aperture fiber Raman spectrum analysis module is connected with a coded aperture fiber array, the coded aperture fiber array is externally connected with a collection fiber, and a collection fiber collimating mirror, a collection fiber coupling mirror and a high-pass Raman filter are sequentially arranged in a transmission light path of the collection fiber; after the excitation optical fiber and the collection optical fiber are converged into a beam at the free end, a Raman signal excitation/collection optical fiber probe is converged at the end part of the free end; the excitation optical fibers in the Raman signal excitation/collection optical fiber probe are positioned at the axis position, and the collection optical fibers are densely distributed by taking the excitation optical fibers as the center.
The coded aperture fiber Raman spectrum analysis module comprises:
the collimating mirror is arranged on an emergent light path of the coded aperture fiber array and used for converting the emergent light of the coded aperture fiber array into parallel light and reflecting the parallel light to the grating at the same incident angle;
the grating is obliquely opposite to the collimating mirror and is used for splitting light while reflecting the parallel light reflected by the collimating mirror onto the focusing mirror so as to enable the parallel light with different wavelengths to form different diffraction angles after being reflected by the grating;
the focusing mirror is obliquely opposite to the grating and is used for focusing the parallel light which is reflected by the grating and has different diffraction angles on the area array detector; and
and the area array detector is arranged on the focal plane of the focusing mirror and is used for receiving the optical signal focused by the focusing mirror.
And a signal processing unit is arranged at the signal output end of the area array detector and is used for carrying out normalization processing on the Raman spectrum signal output by the area array detector.
The coded aperture fiber array is positioned at the focal plane of the collimating mirror in the coded aperture fiber Raman spectrum analysis module.
The coded aperture optical fiber array is provided with optical fibers with equal numbers in the row direction and the column direction, and each optical fiber is connected with one single optical fiber in the collection optical fibers. Each column of optical fibers in the coded aperture optical fiber array adopts different coding forms.
In the Raman spectrum detection, a Raman laser emits exciting light, the exciting light is transmitted through an exciting optical fiber, is collimated through an exciting optical fiber collimating mirror, is filtered through a narrow band filter, is coupled and filtered through an exciting optical fiber coupling mirror, and then enters a Raman excitation/collection probe, the exciting optical fiber is positioned in the center of the exciting/collection probe, the Raman signal collection optical fibers are densely distributed by taking the exciting optical fibers as the center, pass through the collection optical fibers, then sequentially pass through a collection optical fiber collimating mirror and a high-pass Raman filter, are filtered and filtered to remove Rayleigh scattering, are reflected by a sample, pass through the collection optical fibers, and enter a coded aperture Raman spectrum analysis system through a coded aperture array optical fiber.
The coded optical fiber array of the coded aperture spectrum analysis system is positioned at a focal plane of the collimating mirror, light rays enter the grating at a certain angle after passing through the collimating mirror, the distances of the coded optical fibers in each row relative to the center of an optical axis are different, parallel light beams are subjected to certain angle deviation after passing through the collimating mirror, so that the incident angles of the grating are relatively deflected, namely the incident angles of the grating are different, and a plurality of Raman spectrum signals with spectrum micro-deviation are obtained. The bandwidth of the fluorescence signal is much wider than that of the Raman signal of the molecular fingerprint, and the fluorescence signal is hardly influenced by the tiny displacement. Therefore, multiple micro-offset signals can achieve fluorescence background suppression cancellation by differentiation.
The invention can also be realized as follows: a fluorescence background suppression method in Raman spectrum detection comprises the following steps:
a. setting a fluorescence background suppression system in the Raman spectrum detection;
b. after the system is started, arranging a sample to be measured at a position vertical to an emergent light path of the Raman signal excitation/collection optical fiber probe;
c. controlling a Raman laser to emit exciting light, wherein the exciting light respectively irradiates a tested sample through the collimation of an exciting optical fiber collimating mirror, the coupling filtering of an exciting optical fiber coupling mirror and the filtering of a narrow-band filter in the process of transmitting through an exciting optical fiber, and then through a Raman signal exciting/collecting optical fiber probe, and generates a Raman spectrum signal on the tested sample;
d. collecting optical fibers in the Raman signal excitation/collection optical fiber probe collect Raman spectrum signals generated on a tested sample, and the collected Raman spectrum signals are respectively subjected to collimation by a collection optical fiber collimating mirror, coupling filtering by a collection optical fiber coupling mirror and filtering by a high-pass Raman optical filter in the transmission process of the collection optical fibers and then are incident to a coded aperture optical fiber Raman spectrum analysis module through a coded aperture optical fiber array;
e. the coded aperture fiber Raman spectrum analysis module is used for carrying out spectrum analysis on Raman spectrum signals collected by all the collection fibers and outputting a group of Raman spectrum signals with micro spectrum offset;
f. normalizing a group of Raman spectrum signals with micro spectrum deviation by using a signal processing unit to obtain normalized spectrum signal data corresponding to each slit array;
g. and performing Raman spectrum fluorescence background suppression processing on the obtained normalized spectrum signal data corresponding to each slit array by adopting a least square curve fitting difference algorithm and a Lorentz fitting difference processing algorithm, so as to obtain a Raman spectrum with high signal-to-noise ratio.
The Raman spectrum analysis module adopts the coded aperture spectrum analysis module, can simultaneously acquire a plurality of Raman spectrum signals with micro spectral shift in a multi-channel manner, and performs signal data processing by utilizing the difference of the fluorescence spectrum and the molecular fingerprint Raman spectrum on the spectral shift sensitivity, thereby effectively eliminating the interference of the fluorescence background and obtaining the Raman spectrum signals with high signal-to-noise ratio and high reliability in the Raman difference spectrum. The operation of the fluorescence background inhibition method only needs single wavelength excitation and single measurement, the operation is simple and easy, and the reliability of the obtained result is high.
Drawings
FIG. 1 is a schematic diagram of the fluorescent background suppression system of the present invention.
Fig. 2 is a schematic structural diagram of a coded aperture fiber raman spectroscopy analysis module.
FIG. 3 is a flow chart of the fluorescence background suppression method of the present invention.
Detailed Description
As shown in figure 1, the fluorescence background suppression system comprises a Raman laser 1-2, an excitation optical fiber 1-3, a collection optical fiber 1-11, a Raman signal excitation/collection optical fiber probe 1-7, a coded aperture optical fiber array 1-12, a coded aperture optical fiber Raman spectrum analysis module 1-1 and the like. The excitation optical fiber 1-3 is connected with an excitation light output end of the Raman laser 1-2, and an excitation optical fiber collimating mirror 1-4, a narrow band filter 1-5 and an excitation optical fiber coupling mirror 1-6 are sequentially arranged in a transmission light path of the excitation optical fiber 1-3. The coded aperture fiber array 1-12 is connected to the signal input end of the coded aperture fiber Raman spectrum analysis module 1-1, and the collecting fiber 1-11 is connected with the coded aperture fiber array 1-12. The coded aperture optical fiber arrays 1-12 are provided with optical fibers with equal numbers in the row direction and the column direction, and each optical fiber is connected with a single optical fiber in the collection optical fibers 1-11. The transmission light path of the collection optical fiber 1-11 is sequentially provided with a collection optical fiber collimating mirror 1-8, a high-pass Raman optical filter 1-9 and a collection optical fiber coupling mirror 1-10. After the excitation optical fiber 1-3 and the collection optical fiber 1-11 are converged into a beam at the free end, a Raman signal excitation/collection optical fiber probe 1-7 is converged at the end part of the free end. Excitation optical fibers 1-3 in the Raman signal excitation/collection optical fiber probe 1-7 are positioned at the axis position, and the collection optical fibers 1-11 are densely arranged by taking the excitation optical fibers 1-3 as the center.
As shown in FIG. 2, the coded aperture fiber Raman spectrum analysis module 1-1 comprises a collimating mirror 2-1, a grating 2-2, a focusing mirror 2-3 and an area array detector 2-4. The collimating mirror 2-1 is arranged on the emergent light path of the coded aperture fiber array 1-12, and the coded aperture fiber array 1-12 is positioned at the focal plane of the collimating mirror 2-1. The collimator lens 2-1 is used for converting the output light of the coded aperture fiber array 1-12 into parallel light and reflecting the parallel light to the grating 2-2 at the same incident angle. The grating 2-2 is obliquely opposite to the collimating mirror 2-1 and is used for reflecting the parallel light reflected by the collimating mirror 2-1 to the focusing mirror 2-3 and splitting light at the same time, so that the parallel light with different wavelengths forms different diffraction angles after being reflected by the grating 2-2. The focusing mirror 2-3 is obliquely opposite to the grating 2-2 and is used for focusing parallel light which is reflected by the grating 2-2 and has different diffraction angles on the area array detector 2-4. The area array detector 2-4 is arranged on a focal plane of the focusing mirror 2-3 and used for receiving the optical signal focused by the focusing mirror 2-3. And a signal processing unit is arranged at the signal output end of the area array detector 2-4 and is used for carrying out normalization processing on the Raman spectrum signals output by the area array detector.
The coded aperture fiber array 1-12 serves as an incident end of the coded aperture fiber Raman spectrum analysis module 1-1, each column of optical fibers in the fiber array corresponds to a plurality of side-by-side slits of the coded aperture fiber Raman spectrum analysis module 1-1, and each column of optical fibers has different coding forms, preferably Hadamard coding forms. The Raman spectrum signals enter a coded aperture fiber Raman spectrum analysis module 1-1 through a coded aperture fiber array 1-12 of the Hadamard code, and pass through a collimating mirror 2-1, a grating 2-2, a focusing mirror 2-3 and an area array detector 2-4 in the coded aperture fiber Raman spectrum analysis module 1-1 to obtain original Raman spectrum signals carrying spectral information of optical fibers of all units. And sequentially carrying out Hadamard inverse transformation on each row of detection signals of the area array detectors 2-4 in the spectral dimension direction vertical to the grating light splitting, and decoupling to obtain the spectral distribution information of each row of optical fibers. The distances of the coding optical fibers of each column relative to the center of the optical axis are different, and after the coding optical fibers are collimated by the collimating lens 2-1 into parallel beams, the parallel beams are subjected to certain angle deviation, so that the incident angles of the parallel beams on the grating 2-2 are relatively deflected, namely the incident angles of the grating are different, and a plurality of Raman spectrum signals with spectrum micro-deviation can be obtained.
In the fluorescence background suppression system, a Raman laser 1-2 emits exciting light, and the exciting light is collimated by an exciting optical fiber collimating mirror 1-4, filtered by a narrow band filter 1-5, further coupled and filtered by an exciting optical fiber coupling mirror 1-6 and then enters a Raman signal excitation/collection optical fiber probe 1-7 in the transmission process of an exciting optical fiber 1-3. In the Raman signal excitation/collection optical fiber probe 1-7, the excitation optical fibers 1-3 are located at the axial center position, and the collection optical fibers 1-11 are closely arranged around the excitation optical fibers 1-3. In the transmission process of the collection optical fibers 1-11, a plurality of Raman spectrum signals collected by the collection optical fibers 1-11 are sequentially collimated by a collection optical fiber collimating mirror 1-8, filtered by a high-pass Raman optical filter 1-9, filtered by a collection optical fiber coupling mirror 1-10 to remove Rayleigh scattering and sample reflection, transmitted to a coded aperture optical fiber array 1-12 through the collection optical fibers 1-11, and enter a coded aperture optical fiber Raman spectrum analysis module 1-1 through the coded aperture optical fiber array 1-12. The coded aperture fiber arrays 1-12 group a plurality of collection fibers, each row of fibers is a group and corresponds to a certain spectrum micro-offset Raman spectrum signal, and a plurality of rows of coded fiber arrays correspond to a plurality of collection Raman spectrum signals with different spectrum offsets.
The working principle of the coded aperture Raman spectrum fluorescence background suppression technology is a differential Raman spectrum analysis technology, the bandwidth of a fluorescence signal is much larger than that of a molecular fingerprint Raman spectrum signal, the influence of micro-spectrum displacement on the Raman spectrum distribution is far smaller than that of the Raman spectrum signal, and based on the characteristic, the suppression of the fluorescence background can be carried out through the difference of a plurality of micro-offset signals. And the micro-offset signal difference algorithm can adopt a least square curve fitting difference algorithm or a Lorentz fitting difference processing algorithm.
As shown in fig. 3, the fluorescent background suppression method of the present invention is implemented based on the fluorescent background suppression system of the present invention, and specifically includes the following steps:
step 1, starting the system, and arranging the sample to be measured at a position vertical to an emergent light path of the Raman signal excitation/collection optical fiber probe 1-7.
And 2, controlling the Raman laser 1-2 to emit exciting light, wherein the emitted exciting light sequentially passes through collimation of an exciting optical fiber collimating mirror 1-4, filtering of a narrow-band optical filter 1-5 and coupling filtering of an exciting optical fiber coupling mirror 1-6 in the process of being transmitted through an exciting optical fiber 1-3, and finally, the exciting light is irradiated on a sample to be measured through a Raman signal excitation/collection optical fiber probe 1-7.
Step 3, collecting the pull of each collecting optical fiber 1-11 simultaneously in the process of irradiating the tested sample by the Raman signal excitation/collection optical fiber probe 1-7Manchester spectrum signal S1，S2……SiIn the transmission process of the collecting optical fibers 1-11, collected Raman spectrum signals are sequentially subjected to collimation through a collecting optical fiber collimating mirror 1-8, filtering through a high-pass Raman optical filter 1-9, coupling filtering through a collecting optical fiber coupling mirror 1-10, and then are incident to a coding aperture optical fiber Raman spectrum analysis module 1-1 through a coding aperture optical fiber array 1-12.
Step 4, the coded aperture fiber Raman spectrum analysis module 1-1 carries out spectrum analysis on the input Raman spectrum signal, and a group of multiple Raman spectrum signals R with micro spectrum offset are output through the area array detector 2-4i。
Step 5, outputting a plurality of Raman spectrum signals R of each optical fiber array with micro spectrum deviation to the area array detector 2-4iThe signal processing unit is used for carrying out normalization processing by adopting a normalization algorithm to obtain normalized Raman spectrum signal data Y corresponding to each slit arrayi。
Step 6, based on the principle of fluorescence background suppression of the differential Raman spectrum, adopting a least square curve fitting difference algorithm, a Lorentz fitting difference processing algorithm and the like to normalize the spectral signal data Y corresponding to each slit array obtained in the step 5iAnd (4) performing Raman spectrum fluorescence background suppression treatment to obtain a Raman spectrum with high signal-to-noise ratio.
Claims (5)
1. A fluorescence background suppression system in Raman spectrum detection is characterized by comprising a Raman laser and a coded aperture fiber Raman spectrum analysis module; the excitation light output end of the Raman laser is connected with an excitation optical fiber, and an excitation optical fiber collimating lens, an excitation optical fiber coupling lens and a narrow-band optical filter are sequentially arranged in a transmission light path of the excitation optical fiber; the signal input end of the coded aperture fiber Raman spectrum analysis module is connected with a coded aperture fiber array, the coded aperture fiber array is externally connected with a collection fiber, and a collection fiber collimating mirror, a collection fiber coupling mirror and a high-pass Raman filter are sequentially arranged in a transmission light path of the collection fiber; after the free end of the excitation optical fiber and the free end of the collection optical fiber are converged into a beam, a Raman signal excitation/collection optical fiber probe is converged at the end part of the free end; excitation optical fibers in the Raman signal excitation/collection optical fiber probe are positioned at the axis position, and the collection optical fibers are densely distributed by taking the excitation optical fibers as the center; optical fibers with the same number in the row direction and the column direction are arranged in the coded aperture optical fiber array, and each optical fiber is connected with one single optical fiber in the collection optical fiber.
2. The system of claim 1, wherein the coded aperture fiber raman spectroscopy module comprises:
the collimating mirror is arranged on an emergent light path of the coded aperture fiber array and used for converting the emergent light of the coded aperture fiber array into parallel light and reflecting the parallel light to the grating at the same incident angle;
the grating is obliquely opposite to the collimating mirror and is used for splitting light while reflecting the parallel light reflected by the collimating mirror onto the focusing mirror so as to enable the parallel light with different wavelengths to form different diffraction angles after being reflected by the grating;
the focusing mirror is obliquely opposite to the grating and is used for focusing the parallel light which is reflected by the grating and has different diffraction angles on the area array detector; and
and the area array detector is arranged on the focal plane of the focusing mirror and is used for receiving the optical signal focused by the focusing mirror.
3. The system of claim 2, wherein a signal processing unit is disposed at the signal output end of the area array detector for performing normalization processing on the raman spectrum signal output by the area array detector.
4. The fluorescence background suppression system in Raman spectroscopy of claim 2 or 3, wherein the coded aperture fiber array is located at a focal plane of the collimating mirror in the coded aperture fiber Raman spectroscopy module.
5. The fluorescence background suppression system for raman spectroscopy of claim 1 wherein each column of the coded aperture fiber array is encoded differently.
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