CN111562252A - Raman detection system based on coaxial dual-wavelength fluorescence elimination - Google Patents
Raman detection system based on coaxial dual-wavelength fluorescence elimination Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 49
- 238000001514 detection method Methods 0.000 title claims abstract description 39
- 238000003379 elimination reaction Methods 0.000 title claims abstract description 14
- 230000008030 elimination Effects 0.000 title claims description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 28
- 239000013307 optical fiber Substances 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000005259 measurement Methods 0.000 claims description 11
- 230000009977 dual effect Effects 0.000 claims 2
- 238000010791 quenching Methods 0.000 claims 2
- 238000001237 Raman spectrum Methods 0.000 abstract description 16
- 230000005284 excitation Effects 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The application aims to provide a coaxial dual-wavelength fluorescence-elimination-based Raman detection system, two laser beams with similar coaxial wavelengths are sequentially used for irradiating the same position of an object to be detected based on a small frequency shift fluorescence excitation proximity principle to obtain two spectrograms with different Raman signals and the same or similar fluorescence backgrounds, and the two spectrograms are subjected to differential processing to obtain fluorescence-elimination Raman spectra. The laser with different wavelengths can be irradiated to the same position of the object to be detected by combining the laser with adjustable wavelength or multiple lasers through the laser beam combiner, and the laser wavelength can be selected in ultraviolet, visible light, near infrared and infrared wave bands. The laser can be conducted by adopting an optical component, an optical fiber or a telescope system for the objects to be measured with different properties. The fluorescence-eliminating Raman detection system avoids detection errors caused by different detection positions and other external conditions; meanwhile, Raman characteristic peaks with weak signals can be effectively reserved, and the accuracy of Raman detection is improved.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a coaxial dual-wavelength fluorescence-eliminating Raman detection system.
Background
When a beam of light is irradiated to an object to be measured, a small part of scattered light has a frequency different from that of the original light wave, the small part of scattered light capable of reflecting molecular vibration and rotation information is called Raman light, and a fingerprint peak of the Raman spectrum formed by the small part of scattered light can specifically reflect information such as chemical bonds and functional groups in the substance, so that the structure of the substance is determined. The Raman spectrum detection technology has the advantages of high detection speed, small sample consumption and the like, is widely applied to the fields of food and medicine monitoring, public safety, medical treatment and health and the like at present, and has great value on qualitative and quantitative analysis and molecular configuration analysis of substances.
Although the Raman spectrum has wide space utilization, the Raman spectrum is a weak light signal and is very susceptible to about 10 times higher than the signal intensity of the Raman spectrum in the detection process6-108Interference of the multiplied fluorescence; even if a specific excitation light wavelength (1064nm) is used to attenuate the fluorescence effect of the object, the presence of the fluorescence background can interfere with the raman analysis, affect the accuracy of the results, and even overwhelm the raman signal.
According to the principle of fluorescence generation: the fluorescence photon energy is the energy level difference between the lowest energy level of the first electronic excited state and each of the vibration and rotation energy levels of the ground state, so that in a certain wavelength range, the fluorescence spectrum is only related to the characteristics of the substance and cannot change along with the change of the wavelength of incident light, namely the Kasha's rule Kasha rule; the photon energy of Raman scattering is equal to the energy of incident light plus (or minus) the difference of molecular vibration energy level, i.e. the Raman spectrum is closely related to the exciting light and moves along with the change of incident light wavelength. According to the difference of the two spectra in the wavelength change of the exciting light, two laser with small wavelength difference is adopted to excite a sample to obtain two scattering spectra, and the two scattering spectra are subtracted to obtain the Raman spectrum almost without a fluorescence signal.
The portable fluorescence-eliminating Raman spectrum detection system provided in patent CN105510296A adopts a frequency shift excitation method to eliminate fluorescence signals based on laterally excited dual-wavelength laser.
However, two beams of laser with different wavelengths used by the detection system irradiate different positions of the object to be detected, and due to the fact that the sensitivity of the raman spectrum and the fluorescence spectrum is high, the object to be detected at different positions can generate the raman spectrum and the fluorescence spectrum with different intensities due to factors such as concentration and shape, and the like, the difference spectrum obtained by subtraction still contains partial fluorescence background interference, and detection of the raman spectrum is not facilitated.
Disclosure of Invention
Aiming at the defects or shortcomings of the prior art, the invention designs the coaxial dual-wavelength fluorescence-eliminating Raman spectrum detection system, and the system ensures that incident laser can irradiate the same position of an object to be detected by combining two beams of lasers with similar wavelengths.
The Raman spectrum detection system consists of a wavelength-adjustable laser, an optical component and a spectrometer, wherein: the laser with different wavelengths emitted by the wavelength-adjustable laser at different moments irradiates the same position of an object to be measured through the optical component;
in another structure, the raman spectroscopy detection system comprises a first laser, a second laser, a laser beam combiner, an optical component and a spectrometer, wherein: the laser emitted by the first laser and the laser emitted by the second laser are combined by the laser beam combiner and emitted, and the emergent light irradiates the same position of the object to be measured through the optical component;
the Raman scattering light excited on the surface of the object to be measured is transmitted to the spectrometer through the optical component to measure the Raman spectrum.
Further, the laser wavelength can be selected in the ultraviolet, visible, near infrared and infrared bands.
Furthermore, before the laser reaches the object to be measured, a scanning device can be added in the light path to realize multipoint measurement.
Further, the laser can be focused on the object to be measured through the free space optical assembly for measurement.
Further, the laser can be conducted to an object to be measured through an optical fiber for measurement.
Further, the laser can be focused on the object to be measured through a telescopic system for measurement.
Further, the optical assembly may include, but is not limited to: dichroic filters, optical lens sets, optical fibers, and the like.
Compared with the prior art, the method has the following beneficial effects:
the application provides a raman detection system based on coaxial dual-wavelength fluorescence elimination.
The method comprises the steps of emitting laser with different wavelengths at different moments by a wavelength-adjustable laser, or combining two laser beams with similar wavelengths by a laser beam combiner in sequence and emitting the combined laser beams, and carrying out differential processing on two Raman spectrograms with different wavelengths obtained at the same position by utilizing the principle that small frequency shift excites the same or similar fluorescence backgrounds, so as to subtract the same or similar fluorescence backgrounds, and obtain the Raman spectrogram without fluorescence interference.
The system can ensure that two lasers with similar wavelengths irradiate the same position of the object to be detected under the same environmental condition, thereby avoiding detection errors caused by different detection positions and other external condition changes; the fluorescence elimination method provided by the system can effectively retain the Raman characteristic peak with weak signal, and improve the accuracy of Raman detection.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1: the application is a schematic diagram of a coaxial dual-wavelength fluorescence-eliminating Raman detection system based on a wavelength-tunable laser in one embodiment;
FIG. 2: in one embodiment of the application, a coaxial dual-wavelength fluorescence-eliminating Raman detection system based on multi-laser beam combination is shown schematically;
reference numerals: the device comprises a wavelength-adjustable laser 1, a dichroic filter 2, an optical lens group 3, an object to be measured 4, a spectrometer 5, a first laser 6, a second laser 7 and a laser beam combiner 8.
Detailed Description
The conception, the specific structure, and the technical effects produced by the present invention will be further described in conjunction with the accompanying drawings to fully understand the objects, the features, and the effects of the present invention, but the present invention is not limited to the following specific implementation methods.
The present application is described in further detail below with reference to the attached figures.
Fig. 1 shows a specific working mode and working principle of the coaxial dual-wavelength fluorescence-eliminating raman detection system based on the wavelength tunable laser according to the present application, and the system is composed of the wavelength tunable laser, a dichroic filter 2, an optical lens group 3, an object to be detected 4 and a spectrometer 5.
Fig. 2 shows a specific working mode and working principle of the coaxial dual-wavelength fluorescence-eliminating raman detection system based on multi-laser beam combination of the present application, and the system is composed of a first laser 6, a second laser 7, a laser beam combiner 8, a dichroic filter 2, an optical lens group 3, an object to be measured 4, and a spectrometer 5.
Two beams of laser with similar coaxial wavelengths emitted by a laser are reflected by a dichroic filter 2 and vertically enter an optical lens group 3 of an object to be detected, laser light is converged by the optical lens group 3 and then irradiates the same position of the object to be detected 4, Raman scattered light excited on the surface of the object to be detected 4 is converged by the optical lens group 3 and then penetrates through the dichroic filter 2, and finally the two spectrums are intensively transmitted to a spectrograph 5, the spectrograph 5 obtains two spectrograms with different Raman signals but same or similar fluorescence backgrounds, the two spectrograms are subjected to differential processing, and the fluorescence backgrounds are reduced to obtain the Raman signals.
Wherein the reflection point of the emergent laser on the dichroic filter 2 is the 2 midpoint of the dichroic filter; the detection point of the object to be detected 4 and the middle point of the dichroic filter 2 are both positioned on the axis of the optical lens group 3.
The laser wavelength can be selected in ultraviolet, visible, near infrared and infrared bands.
Before the laser reaches the object to be measured, a scanning device is added in the light path to realize multipoint measurement.
The laser can be conducted to an object to be measured through an optical fiber for measurement.
The laser can be focused on the object to be measured through a telescopic system for measurement.
Application example 1:
as shown in fig. 1, a coaxial dual-wavelength fluorescence-eliminating raman detection system based on a wavelength-tunable laser includes: the device comprises a wavelength-adjustable laser 1, a dichroic filter 2, an optical lens group 3, an object to be measured 4 and a spectrometer 5. The wavelength-adjustable laser 1 adopts a low-power tunable pulse titanium gem laser with an eastern flash model TUN-Ti-770-840, and can modulate the laser wavelength in the range of 770-840 nm. The long-range-rich technology F86-322 dichroic filter 2 is adopted, and the filter can reflect incident light with the wavelength of 450nm-790nm and transmit light with the wavelength of 814nm-1100 nm.
The wavelength-adjustable laser 1 is adjusted to emit 780nm laser and 785nm laser in sequence, the lasers are reflected by the dichroic filter 2 and converged into the optical lens group 3, and the optical lens group 3 converges the lasers and irradiates the lasers to the same position of the object to be measured 4. Raman scattered light with two wavelengths excited by the surface of the object to be measured 4 is focused by the optical lens group 3 and is transmitted to the spectrometer 5 through the dichroic filter 2, and a Raman light signal received by the spectrometer 5 is 814-1100 nm. The optical signal is converted into an electrical signal inside the spectrometer 5 for raman spectroscopy. The obtained Raman spectrogram with the exciting light of 780nm and the Raman spectrogram with the exciting light of 785nm have basically the same fluorescence background noise, but the wavelength position of the Raman peak position is obviously changed,
and carrying out differential operation on the data of the two images to finally obtain the fluorescence-eliminating Raman spectrum data of the object to be detected 6.
Application example 2:
as shown in fig. 2, a coaxial dual-wavelength fluorescence-eliminating raman detection system based on multi-laser combined beam includes: 780nm laser 6 and 785nm laser 7, which can emit 780nm laser and 785nm laser; the laser beam combiner 8 is a LightHUB compact laser beam combiner adopting Bowei technology, and can combine laser beams within the range of 375-; the dichroic filter 2 is also manufactured by Changchi technology and can reflect light with a wavelength of 450nm-790nm and transmit light with a wavelength of 814nm-1100 nm.
The two lasers transmit laser into a laser beam combiner 8 through a conducting optical fiber, and the emergent combined laser is reflected by a dichroic filter 2 and focused by an optical lens group 3 and then sequentially irradiates the same position of an object to be measured 4.
The Raman scattered light excited on the surface of the object to be measured 4 is converged by the optical lens group 3, then passes through the dichroic filter 2, and is focused at the optical signal receiving position of the spectrometer 5, and the spectrometer 5 can receive the Raman scattered light with the wavelength within the range of 814nm-1100 nm.
And performing differential processing on 780nm spectral data and 785nm spectral data obtained by analyzing by the spectrometer 5 to obtain a fluorescence-eliminating Raman spectrogram of the object 4 to be detected at the position.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. A coaxial dual-wavelength fluorescence elimination-based Raman detection system is characterized in that two beams of lasers with similar coaxial wavelengths irradiate the same position of an object to be detected to obtain two spectrograms with different Raman signals and the same or similar fluorescence backgrounds, the two spectrograms are subjected to differential processing, the fluorescence backgrounds are subtracted, and the Raman signals are obtained.
2. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system of claim 1, wherein the two lasers can be lasers with different wavelengths emitted by a laser with adjustable wavelength.
3. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system of claim 1, wherein the two lasers can be two lasers or a combination of more lasers.
4. The Raman detection system based on coaxial dual-wavelength fluorescence elimination as recited in claim 3, wherein the laser beams emitted by the two or more lasers need to be combined by the laser beam combiner and then irradiated onto the object to be detected.
5. The coaxial dual wavelength fluorescence-quenching based raman detection system of claim 1, wherein said laser can be in the ultraviolet, visible, near infrared and infrared bands.
6. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system according to claim 1, wherein the laser can realize multi-point measurement by adding a scanning device in the optical path before reaching the object to be detected.
7. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system of claim 1, wherein the laser can be focused on the object to be measured through a free-space optical component for measurement.
8. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system of claim 1, wherein the laser can be conducted to an object to be measured through an optical fiber for measurement.
9. The coaxial dual-wavelength fluorescence-elimination-based Raman detection system according to claim 1, wherein the laser can be focused on the object to be detected through a telescopic system for measurement.
10. The coaxial dual wavelength fluorescence-quenching-based raman detection system of claim 7, wherein said optical components can include but are not limited to: dichroic filters, optical lens sets, optical fibers, and the like.
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Cited By (4)
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| CN112147125A (en) * | 2020-09-16 | 2020-12-29 | 北京华泰诺安探测技术有限公司 | Fluorescence inhibition method, device, storage medium and computer equipment |
| CN112869691A (en) * | 2021-02-03 | 2021-06-01 | 清华大学 | Dual-wavelength enhanced Raman endoscopic noninvasive pathology detection device and detection method |
| CN114660037A (en) * | 2022-05-23 | 2022-06-24 | 山东交通学院 | Oil film measuring device and method based on differential Raman composite fluorescence spectrum |
| CN115079181A (en) * | 2021-03-12 | 2022-09-20 | 欧姆龙(上海)有限公司 | Photoelectric sensor and object detection method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112147125A (en) * | 2020-09-16 | 2020-12-29 | 北京华泰诺安探测技术有限公司 | Fluorescence inhibition method, device, storage medium and computer equipment |
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| CN112869691A (en) * | 2021-02-03 | 2021-06-01 | 清华大学 | Dual-wavelength enhanced Raman endoscopic noninvasive pathology detection device and detection method |
| CN115079181A (en) * | 2021-03-12 | 2022-09-20 | 欧姆龙(上海)有限公司 | Photoelectric sensor and object detection method |
| CN114660037A (en) * | 2022-05-23 | 2022-06-24 | 山东交通学院 | Oil film measuring device and method based on differential Raman composite fluorescence spectrum |
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