Multi-wavelength corrected raman fluorescence spectrum combined detection device and method

Abstract

The application provides a multi-wavelength correction Raman fluorescence spectrum combined detection device and method, a plurality of wavelength light sources are used to simultaneously perform Raman and fluorescence spectrum detection, Raman and fluorescence spectrum signals excited by the plurality of wavelength light sources are analyzed and mutually corrected, more accurate Raman frequency shift and fluorescence spectrum of a detected substance are obtained, and detection precision is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of spectral detection, and particularly relates to a multi-wavelength corrected Raman fluorescence spectrum combined detection device and method. BACKGROUND

[0002] Raman and fluorescence spectrum detection are commonly used means for detecting substances. Raman spectrum is obtained based on Raman effect between excitation spectrum and molecules to be detected. Raman spectrum measures vibration and rotation of molecules, and Raman frequency shift size is irrelevant to wavelength of an incident light source. Therefore, Raman spectrum is called “molecular fingerprint”. As a powerful means for detecting molecules, Raman spectrum technology can realize rapid and non-destructive detection of samples. Fluorescence spectrum method is used for analyzing organic substances capable of generating fluorescence signals, and is also an important qualitative and quantitative spectrum analysis means.

[0003] Intensity of a Raman spectrum signal is inversely proportional to fourth power of wavelength of an excitation light source. The shorter the wavelength of the excitation light source, the stronger the Raman signal, but the stronger the fluorescence interference. The longer the wavelength of the excitation light source, the weaker the fluorescence interference, but the weaker the Raman signal. Traditional spectrum detection usually uses a single wavelength, and it is difficult to simultaneously consider Raman and fluorescence signals. Even if the signals are separated through data processing methods, accuracy is difficult to guarantee. SUMMARY

[0004] To solve the above technical problems, the present application provides a multi-wavelength corrected Raman fluorescence spectrum combined detection device and method. Multiple wavelength light sources are used to simultaneously perform Raman and fluorescence spectrum detection. Raman and fluorescence spectrum signals excited by multiple wavelengths are analyzed and corrected with each other, so that more accurate Raman frequency shift and fluorescence spectrum of a detected substance are obtained, and detection accuracy is improved.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A multi-wavelength corrected Raman fluorescence spectrum combined detection device comprises a 266nm laser, a 532nm laser and a 785nm laser, an emission optical fiber, a receiving optical fiber, a filter lens group, a fluorescence spectrometer and a Raman spectrometer. Laser emitted by the 266nm laser, the 532nm laser and the 785nm laser enters a sample cell through a three-in-one emission optical fiber. Fluorescence and Raman scattered light excited in the sample cell first pass through the filter lens group to filter out influence of 266nm, 532nm and 785nm wavelength lasers on subsequent detection, and then pass through a two-in-one receiving optical fiber to enter the fluorescence spectrometer and the Raman spectrometer, respectively.

[0007] Furthermore, the filter group consists of a 266nm notch plate, a 532nm notch plate and a 785nm notch plate, the spectral range of the fluorescence spectrometer is 270nm~1100nm, and the spectral range of the Raman spectrometer is 100cm -1 ~4000cm -1 .

[0008] The present invention also provides a multi-wavelength corrected Raman fluorescence spectroscopy combined detection method, comprising the following steps:

[0009] Step 1: Turn on the 266nm laser, turn off the 532nm laser and the 785nm laser, and use the fluorescence spectrometer to collect the spectrum signal: , the Raman spectrometer collects spectral signals as ;

[0010] Step 2: Turn on the 532nm laser, turn off the 266nm laser and the 785nm laser, and use the fluorescence spectrometer to collect the spectrum signal: , the Raman spectrometer collects spectral signals as ;

[0011] Step 3: Turn on the 785nm laser, turn off the 266nm laser and the 532nm laser, and collect the spectrum signal of the fluorescence spectrometer as follows: , the Raman spectrometer collects spectral signals as ;

[0012] Step 4: 、 and Perform filtering respectively to obtain 、 and ;

[0013] Step 5: 、 and After normalization, the average value is added to obtain the spectral signal ;

[0014] Step 6: 、 and Perform filtering respectively to obtain 、 and ;

[0015] Step 7 minus Medium 100cm -1 ~4000cm -1 The corresponding wavelength value is obtained ; Subtract Middle 100 cm -1 ~4000 cm -1 The value of the corresponding wavelength, get ; Subtract Middle 100 cm -1 ~4000 cm -1 The value of the corresponding wavelength, get ;

[0016] Step 8, peak search is carried out on , get m peak wave number sequence[ , … ], peak search is carried out on , get n peak wave number sequence[ , … ], peak search is carried out on , get k peak wave number sequence[ , … ]; m, n and k are integers greater than or equal to 1;

[0017] Step 9, compare sequence[ , … ],[ , … ] and[ , … ], if there is a value that exists in at least two sequences at the same time, it is considered that this value is the measured Raman peak value, the sequence of such values is[ , … ], where j is an integer greater than or equal to 1; then[ , … ] is the multiple Raman peak value of the measured substance;

[0018] Step 10, the wavelength corresponding to[ , … ] in the spectrum signal is smoothed to eliminate the Raman peak in the fluorescence spectrum, and the spectrum signal is obtained; the processed spectrum signal is the fluorescence spectrum of the detected substance.

[0019] Beneficial effects:

[0020] The present application analyzes and corrects Raman and fluorescence spectrum signals excited by multiple wavelengths, makes up the deficiency of spectrum detection under different wavelengths and single wavelength, can simultaneously analyze mixed spectrum information of multiple substances, and obtains more accurate Raman frequency shift and fluorescence spectrum of detected substances, and improves detection precision. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Figure is a schematic diagram of the multi-wavelength corrected Raman fluorescence spectrum combined detection device of the present application;

[0022] Figure 2 Figure is a schematic diagram of an emitting optical fiber;

[0023] Figure 3 Figure is a schematic diagram of a fourth optical fiber head;

[0024] Figure 4 Figure is a schematic diagram of a receiving optical fiber;

[0025] Figure 5 Figure is a schematic diagram of a seventh optical fiber head;

[0026] Figure 6 Figure is a flow chart of the multi-wavelength corrected Raman fluorescence spectrum combined detection method of the present application. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the present application clearer and more comprehensible, the present application is further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and are not used to limit the present application. In addition, the technical features involved in each embodiment of the present application described below can be combined with each other as long as they do not conflict with each other.

[0028] As Figure 1As shown, the multi-wavelength correction Raman fluorescence spectrum combined detection device of the present application comprises a display control module, a power module, a 266nm laser, a 532nm laser, a 785nm laser, an emitting optical fiber, a receiving optical fiber, a filter lens group, a fluorescence spectrometer and a Raman spectrometer. The display control module is responsible for the control and result display of the whole device, and is connected with the 266nm laser, the 532nm laser, the 785nm laser, the fluorescence spectrometer and the Raman spectrometer. The power module is responsible for the power supply of other devices, and is connected with the display control module, the 266nm laser, the 532nm laser, the 785nm laser, the fluorescence spectrometer and the Raman spectrometer. The 266nm laser, the 532nm laser and the 785nm laser are connected with a three-in-one emitting optical fiber through an SMA905 joint, and the other end of the emitting optical fiber is connected with a sample cell through an SMA905 joint. One end of a two-in-one receiving optical fiber is connected with the filter lens group through an SMA905 joint, and the other end is connected with the fluorescence spectrometer and the Raman spectrometer through SMA905 joints. The laser emitted by the 266nm laser, the 532nm laser and the 785nm laser enters the sample cell through the three-in-one emitting optical fiber, the fluorescence and Raman scattering light excited in the sample cell first passes through the filter lens group to filter out the influence of 266nm, 532nm and 785nm wavelength laser on the subsequent detection, and then enters the fluorescence spectrometer and the Raman spectrometer through the two-in-one receiving optical fiber. The filter lens group is composed of a 266nm notch filter, a 532nm notch filter and a 785nm notch filter, the spectral range of the fluorescence spectrometer is 270nm~1100nm, and the spectral range of the Raman spectrometer is 100cm -1 ~4000cm -1 .

[0029] The emitting optical fiber comprises a first optical fiber head 1, a second optical fiber head 2, a third optical fiber head 3, a fourth optical fiber head 4, a first beam combiner 5, a first optical fiber 6, a second optical fiber 7, a third optical fiber 8 and a fourth optical fiber 9. Figure 2 The first optical fiber head 1, the second optical fiber head 2, the third optical fiber head 3 and the fourth optical fiber head 4 are standard SMA905 optical fiber joints. The first optical fiber 6, the second optical fiber 7 and the third optical fiber 8 are optical fibers with a core diameter of 200μm and a spectral transmittance of 260nm to 1100nm of more than 80%. One end of the first optical fiber 6, the second optical fiber 7 and the third optical fiber 8 is connected with the first optical fiber head 1, the second optical fiber head 2 and the third optical fiber head 3 respectively, and the other end is combined into the fourth optical fiber 9 through the first beam combiner 5. The fourth optical fiber 9 contains three optical fibers with a core diameter of 200μm and a spectral transmittance of 260nm to 1100nm of more than 80%. The fourth optical fiber 9 is connected with the fourth optical fiber head 4. Figure 3 As shown in the fourth optical fiber head 4 end face, the end faces of the three 200μm optical fibers are evenly distributed in a triangular shape on the end face of the fourth optical fiber head 4.

[0030] The receiving optical fiber comprises a first optical fiber head 1, a second optical fiber head 2, a third optical fiber head 3, a fourth optical fiber head 4, a first beam combiner 5, a first optical fiber 6, a second optical fiber 7, a third optical fiber 8 and a fourth optical fiber 9.Figure 4 As shown, it includes a fifth optical fiber head 10, a sixth optical fiber head 11, a seventh optical fiber head 12, a second combiner 13, a fifth optical fiber 14, a sixth optical fiber 15 and a seventh optical fiber 16. The fifth optical fiber head 14, the sixth optical fiber head 15 and the seventh optical fiber head 16 are standard SMA905 optical fiber connectors. The fifth optical fiber 10 and the sixth optical fiber 11 are optical fibers with a core diameter of 600μm and a spectral transmittance of more than 80% from 260nm to 1100nm. One end of the fifth optical fiber 10 and the sixth optical fiber 11 are respectively connected to the fifth optical fiber head 10 and the sixth optical fiber head 11, and the other end is combined into the seventh optical fiber 16 through the second combiner 13. The seventh optical fiber 16 contains two optical fibers with a spectral transmittance of more than 80% at 600μm and 260nm to 1100nm. The seventh optical fiber 16 is connected to the seventh optical fiber head 12. The end face of the seventh optical fiber head 12 is as shown Figure 5 As shown, two 600 μm optical fiber end faces are evenly distributed on the end face of the seventh optical fiber head 12 .

[0031] like Figure 6 As shown, the combined detection method of multi-wavelength corrected Raman fluorescence spectroscopy of the present invention comprises the following steps:

[0032] Step 1: Turn on the 266nm laser, turn off the 532nm laser and the 785nm laser, and use the fluorescence spectrometer to collect the spectrum signal: , the Raman spectrometer collects spectral signals as ;

[0033] Step 2: Turn on the 532nm laser, turn off the 266nm laser and the 785nm laser, and use the fluorescence spectrometer to collect the spectrum signal: , the Raman spectrometer collects spectral signals as ;

[0034] Step 3: Turn on the 785nm laser, turn off the 266nm laser and the 532nm laser, and collect the spectrum signal of the fluorescence spectrometer as follows: , the Raman spectrometer collects spectral signals as ;

[0035] Step 4: 、 and Filter them separately to get 、 and ;

[0036] Step 5: 、 and After normalization, the average value is added to obtain the spectral signal ;

[0037] Step 6: , and are filtered respectively to obtain , and ;

[0038] Step 7, subtracts the value of 100cm -1 ~4000cm -1 corresponding wavelength in to obtain , subtracts the value of 100cm -1 ~4000cm -1 corresponding wavelength in to obtain , subtracts the value of 100cm -1 ~4000cm -1 corresponding wavelength in to obtain ;

[0039] Step 8, peak searching is performed on to obtain m peak wave number sequences[ , … ], peak searching is performed on to obtain n peak wave number sequences[ , … ], and peak searching is performed on to obtain k peak wave number sequences[ , … ]. m, n and k are integers greater than or equal to 1.

[0040] Step 9, sequences[ , … ],[ , … ] and[ , … ] are compared. If a value exists in at least two sequences at the same time, the value is considered as a measured Raman peak value, and the sequence of such values is[ , … ], where j is an integer greater than or equal to 1. Then[ , … ] are multiple Raman peak values of the measured substance.

[0041] Step 10, smoothing the corresponding wavelength in the spectrum signal , , … to eliminate the Raman peak in the fluorescence spectrum, to obtain the signal .

[0042] The processed spectrum signal is the fluorescence spectrum of the detected substance.

[0043] Those skilled in the art will easily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A detection method of a multi-wavelength correction Raman fluorescence spectrum combined detection device, characterized in that, The multi-wavelength correction Raman fluorescence spectrum combined detection device comprises a 266nm laser, a 532nm laser and a 785nm laser, an emitting optical fiber, a receiving optical fiber, a filter lens group, a fluorescence spectrometer and a Raman spectrometer, the laser emitted by the 266nm laser, the 532nm laser and the 785nm laser enters a sample cell through a three-in-one emitting optical fiber, the excited fluorescence and Raman scattering light in the sample cell firstly pass through the filter lens group, the influence of the 266nm, 532nm and 785nm wavelength lasers on subsequent detection is filtered out, and then pass through a two-in-one receiving optical fiber and enter the fluorescence spectrometer and the Raman spectrometer respectively; The detection method comprises the following steps: Step 1, turn on 266nm laser, turn off 532nm laser and 785nm laser, the fluorescence spectrometer collects spectral signal as , the Raman spectrometer collects spectral signal as ; Step 2, turn on 532 nm laser, turn off 266 nm laser and 785 nm laser, the fluorescence spectrometer collects the spectral signal as , the Raman spectrometer collects the spectral signal as ; Step 3, turn on the 785 nm laser, turn off the 266 nm laser and the 532 nm laser, and the fluorescence spectrometer collects the spectral signal as , and the Raman spectrometer collects the spectral signal as ; Step 4, filtering is performed on , and respectively to obtain , and ; Step 5, normalization and averaging of the spectra signals , and ;​ Step 6, filtering the , and respectively, to obtain , and ; Step 7, Subtract 100 cm -1 ~ 4000 cm -1 corresponding wavelength values, resulting in ; Subtract 100 cm -1 ~ 4000 cm -1 corresponding wavelength values, resulting in ; Subtract 100 cm -1 ~ 4000 cm -1 corresponding wavelength values, resulting in ; Step 8: Perform peak search and obtain m peak wave number sequences [ , … ],right Perform peak search and obtain n peak wave number sequences [ , … ],right Perform peak search and obtain k peak wave number sequences [ , … ]; m, n and k are integers greater than or equal to 1; Step 9, comparing sequences , … ], , … ] and , … ] if there is a value that exists in at least two sequences at the same time, then the value is considered to be a measured Raman peak value, and the sequence of such values is , … ] where j is an integer greater than or equal to 1; then , … ] is a plurality of Raman peak values of the measured substance. Step 10, smoothing the corresponding wavelength in the spectrum signal , , … ] to eliminate the Raman peak in the fluorescence spectrum, obtaining the spectrum signal ; the processed spectrum signal is the fluorescence spectrum of the detected substance.

2. The method of claim 1, wherein: The filter mirror group is composed of a 266nm notch filter, a 532nm notch filter and a 785nm notch filter, the spectral range of the fluorescence spectrometer is 270nm-1100nm, and the spectral range of the Raman spectrometer is 100cm -1 -4000cm -1 .

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