CN110174393A - A kind of difference single photon Raman sensing quick and precisely detects the device and its detection method of wheat vomitoxin - Google Patents

A kind of difference single photon Raman sensing quick and precisely detects the device and its detection method of wheat vomitoxin Download PDF

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CN110174393A
CN110174393A CN201910568001.9A CN201910568001A CN110174393A CN 110174393 A CN110174393 A CN 110174393A CN 201910568001 A CN201910568001 A CN 201910568001A CN 110174393 A CN110174393 A CN 110174393A
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laser
single photon
semi
photodetector
collimator
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CN110174393B (en
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翁士状
张雪艳
徐超
唐佩佩
朱文秀
袁和财
张东彦
郑玲
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Anhui University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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Abstract

The present invention relates to devices and its detection method that a kind of difference single photon Raman sensing quick and precisely detects wheat vomitoxin, and the device includes optical fiber laser, optical fiber collimator, semi-transparent semi-reflecting lens, sample cell, photodetector, optical filter, single photon counter and optical signal obtaining module.The present invention improves Raman using single photon counter and senses sensitivity, in conjunction with displacement difference removal fluorescence background and light source interference, fast and accurately realizes the detection to vomitoxin in wheat.

Description

A kind of difference single photon Raman sensing quick and precisely detects the device of wheat vomitoxin And its detection method
Technical field
The present invention relates to crops quality security fields, quick and precisely more particularly to a kind of difference single photon Raman sensing Detect the device and its detection method of wheat vomitoxin.
Background technique
Head blight is by one of main disease of the microbial wheat of F.graminearum schw, which often causes the wheat substantially underproduction (general up to 10%~20%), or even total crop failure;The vomitoxin secreted in Fusarium graminearum infection processs simultaneously (Deoxynivalenol, DON) has biggish harm to people and animals, can cause dizziness, nausea and diarrhea etc., influences to exempt from when serious Epidemic disease power and fertility etc..Vomitoxin becomes the chief threat of wheat increase yield and quality safety, at present in China's regulation cereal Limit standard is 1mg/kg.Vomitoxin belongs to trichothecene, highly stable in food processing, and considers to deposit Popularity, need development method realize its quickly detect.The methods of traditional detection method such as gas phase liquid chromatography, mass spectrum, Pre-processing is complicated, quantitative precision is high, time-consuming for detection, operation profession, it is difficult to meet online detection requirements;Spectrographic technique is such as Though Raman spectrum, high light spectrum image-forming and infrared spectroscopy etc. are quick and easy, detection sensitivity is lower.Therefore, development is suitble to inspection The fast method of trace vomitoxin and device in wheat is surveyed to be of great significance.
Summary of the invention
In order to solve the problems, such as that the weak and existing signal Raman of Raman spectrum sensitivity existing for crops nocuousness analyte detection increases Stability problem in strong method, the present invention improve Raman using single photon counter and sense sensitivity, in conjunction with displacement difference removal Fluorescence background and light source interference, provide a kind of difference single photon Raman sensing quick and precisely detect wheat vomitoxin device and Its detection method fast and accurately realizes the detection to vomitoxin in wheat.
The device that a kind of difference single photon Raman sensing of the present invention quick and precisely detects wheat vomitoxin is specific Technical solution is as follows: including (optical fiber) laser, optical fiber collimator, semi-transparent semi-reflecting lens, sample cell, photodetector, optical filter, Single photon counter and optical signal obtaining module.
(optical fiber) laser of the present invention includes the first, second laser.Wherein, first laser device swashs for 638nm Light device, peak power output 140mW, intensity tuning range are 1~100%;Second laser is 633nm laser, maximum Output power is 80mW, and intensity tuning range is also 1~100%.Two lasers are opened in timesharing, realize swashing for different wave length Hair.Optical fiber collimator is coupled with laser, obtains corresponding parallel laser.
Semi-transparent semi-reflecting lens response range of the present invention is 380-780mm, and realization laser 90% penetrates, 10% laser is anti- It penetrates.Wherein, the laser after reflection is perceived by photodetector, the Strength Changes for writing laser;The laser of transmission shines Sample cell is penetrated, its Raman response is excited.
Photodetector (two) of the present invention are side window shape of the mouth as one speaks multialkali photoca PMT (1914F), TE refrigeration, light Spectrum response range is 190-860nm.The sample cell is the quartz colorimetric utensil of four sides light passing, outer dimension 12.5*12.5* 45mm, light path 10*10mm.The laser of different light sources after semi-transparent semi-reflecting lens, felt by photodetector by the laser of reflection Know.
The optical filter is BP700 bandpass filter, its central wavelength is 700nm, bandwidth 10nm, half peak strip Width is 45nm, to pass through 703nm Raman response signal.
The single photon counter is SPCM-AQRH, and monitoring wave-length coverage is 400nm to 1060nm.What sample issued Peak value 703nm Raman response after optical filter, perceived by single photon counter.
Optical signal obtaining module of the present invention has the function of I/V conversion, filtering and amplification, by photodetector Corresponding voltage value is obtained after amplification with the current value of single photon counter output by I/V conversion, filtering.
Data analysis and processing unit (module) of the present invention completes two photodetectors, photon counters through photoelectricity Signal extraction module converts the collection of signal and constructs the regression model of collection capacity and vomitoxin content, completion pair The prediction of its concentration.
A kind of difference single photon Raman sensor of the present invention quick and precisely detects the detection method of wheat vomitoxin, i.e. institute Vomitoxin detection method is as follows in the head blight wheat of building: 1) crushing the wheat of head blight, ethyl alcohol is added, by super It obtains being detected liquid sample after sound, centrifugation removal supernatant;2) golden stick Nano sol is concentrated, mix, is put into ratio after addition NaCl In color ware;3) first laser device is opened, laser first passes through first laser collimator, then by semi-transparent semi-reflecting lens, by semi-transparent half The light reflected when anti-mirror is perceived by photodetector, and the electric signal of output is using defeated after the conversion of optical signal obtaining module V out1, the laser irradiation sample cell of transmission excites its Raman response.The Raman response that sample issues is after optical filter, coverlet Photon counter is perceived.The current value of single photon counter output exports v ' after the conversion of optical signal obtaining moduleIt is single, close Close first laser device;4) second laser is opened, for step with 3), optical signal obtaining module exports v2、v”It is single;5) using using partially Least square regression buildingThe dose-effect relationship of vomitoxin content in bivector and head blight wheat.
Compared with prior art, there are following technical effects by the present invention: introducing single photon counter as Raman signal Sension unit promotes sensitivity;The excitation of timesharing dual wavelength is carried out using tunable narrow-band laser light source, difference obtains tie substance Raman response removal fluorescence background and light source interference;Establish the amount of Raman signal, excitation intensity background material and target molecule Effect relationship solves the problems, such as in the weak and existing signal enhancing method of Raman spectrum sensitivity existing for crops nocuousness analyte detection Stability problem.
Detailed description of the invention
Fig. 1 is the structural representation for the device that difference single photon Raman sensing of the present invention quick and precisely detects wheat vomitoxin Figure;
Fig. 2 is that difference single photon Raman of the present invention senses the inspection for quick and precisely detecting the device of wheat vomitoxin Survey method flow diagram;
Fig. 3 is the circuit diagram of optical signal obtaining module of the present invention.
Specific embodiment
Below with reference to Fig. 1, the present invention is described in further detail.
Refering to fig. 1, a kind of difference single photon Raman sensing quickly detects the device of wheat vomitoxin, including first laser Device 10, second laser 20, first laser collimator 30, second laser collimator 40, semi-transparent semi-reflecting lens 50, the first photodetection Device 51, the second photodetector 52, optical signal obtaining module 53, data analysis and processing unit 54, sample cell 60, optical filter 70, single photon counter 80.
Optical fiber laser includes first laser device 10, second laser 20;Wherein, first laser device 10 is 638nm laser Device, peak power output 140mW, intensity tuning range are 1~100%;Second laser 20 is 633nm laser, maximum Output power is 80mW, and intensity tuning range is also 1~100%;
Optical fiber collimator includes first laser collimator 30, second laser collimator 40;
Photodetector includes the first photodetector 51, the second photodetector 52;
Sample cell 60 is transparent cuvette;It preferably, is the quartz colorimetric utensil of four sides light passing, outer dimension 12.5* 12.5*45mm light path 10*10mm.
First laser device 10 connect with first laser collimator 30 and is coupled, and the second laser 20 and second swashs The connection of optical collimator 40 is coupled;First laser collimator 30, second laser collimator 40 light output end be provided with half Saturating semi-reflective mirror 50, first laser collimator 30, second laser collimator 40 light output end semi-transparent semi-reflecting lens 50 reflection position The first photodetector 51, the second photodetector 52 is respectively set;First photodetector 51, second photodetector 52 Signal output end connects optical signal obtaining module 53;The light output end of first laser collimator 30, second laser collimator 40 The transmission positions of semi-transparent semi-reflecting lens 50 sample cell 60 is set, transmitted light using optical filter 70 is transmitted to monochromatic light by sample cell 60 Sub-count device 80 is connected with data analysis and processing unit 54, the photosignal in the optical signal obtaining module 53 Extraction module 53 is connect with single photon counter 80.
Data analysis and processing unit 54 is that the voltage value of optical signal obtaining module 53 is connected to PC by voltage acquisition plate End, then carries out establishing least square model unit again;The data analysis and processing unit 54 completes the first photodetector 51,52 two photodetectors of the second photodetector, single photon counter 80 are converted through optical signal obtaining module 53 The collection of signal and the regression model for constructing collection capacity and vomitoxin content complete the prediction to its concentration.
After wheat is extracted, after acquisition extracting solution is put into cuvette, first, second laser 10 and 20 point Shi Kaiqi, realizes the excitation of different wave length, and two beam Laser Time Sharings are parallel by that can obtain after the first, second laser aligner 30 and 40 Light beam.After two beam Laser Time Sharings pass through semi-transparent semi-reflecting lens 50, the laser after reflection is by the first, second institute of photodetector 51 and 52 The electric signal of perception, output obtains corresponding output valve v after optical signal obtaining module 531、v2.The laser of transmission shines Sample cell 60 is penetrated, its Raman response is excited.The Raman response that sample issues is after optical filter 70, by 80 institute of single photon counter Perception.The current value that single photon counter 80 exports exports v ' after optical signal obtaining moduleIt is single、v”It is single
Referring to Fig.2, a kind of difference single photon Raman sensing for also disclosing a kind of foregoing device in the present invention is fast The method of speed detection wheat vomitoxin includes the following steps: 1) to crush the wheat of head blight, ethyl alcohol is added, by ultrasound, It obtains being detected liquid sample after centrifugation removal supernatant;2) golden stick Nano sol is concentrated, mix, is put into cuvette after addition NaCl In;3) first laser device 10 is opened, laser first passes through first laser collimator 30, then by semi-transparent semi-reflecting lens 50, process is semi-transparent The light reflected when semi-reflective mirror is perceived by photodetector 51, and the electric signal of output is using 53 turns of optical signal obtaining module V is exported after changing1, the laser irradiation sample cell 60 of transmission excites its Raman response.The Raman response that sample issues passes through optical filter After 70, perceived by single photon counter 80.The current value of single photon counter output passes through 53 turns of optical signal obtaining module V ' is exported after changingIt is single, close first laser device 10;4) second laser 20 is opened, with 3), optical signal obtaining module 53 exports step v2、v”It is single;5) it is constructed using using Partial Least Squares RegressionVomitoxin content in bivector and head blight wheat Dose-effect relationship.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.

Claims (8)

1. the device that a kind of difference single photon Raman sensing quick and precisely detects wheat vomitoxin, which is characterized in that including light Fibre laser, optical fiber collimator, semi-transparent semi-reflecting lens (50), sample cell (60), photodetector, optical filter (70), single photon meter Number device (80) and optical signal obtaining module (53);
The optical fiber laser includes first laser device (10), second laser (20);Wherein, first laser device (10) is 638nm laser, peak power output 140mW, intensity tuning range are 1~100%;Second laser (20) is 633nm Laser, peak power output 80mW, intensity tuning range are also 1~100%;
The optical fiber collimator includes first laser collimator (30), second laser collimator (40);
The photodetector includes the first photodetector (51), the second photodetector (52);
The sample cell (60) is transparent cuvette;
The first laser device (10) is connect with first laser collimator (30) to be coupled, the second laser (20) It connect and is coupled with second laser collimator (40);First laser collimator (30), the light of second laser collimator (40) are defeated Outlet is provided with semi-transparent semi-reflecting lens (50), the light output end of first laser collimator (30), second laser collimator (40) The first photodetector (51), the second photodetector (52) is respectively set in the reflection position of semi-transparent semi-reflecting lens (50);First photoelectricity Signal output end connection optical signal obtaining module (53) of detector (51), the second photodetector (52);First laser is quasi- Straight device (30), second laser collimator (40) the transmission position of semi-transparent semi-reflecting lens (50) of light output end sample cell (60) are set, Transmitted light is transmitted to single photon counter (80), the optical signal obtaining using optical filter (70) by sample cell (60) It is connected in module (53) data analysis and processing unit (54), the optical signal obtaining module (53) and single photon counter (80) it connects.
2. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that semi-transparent semi-reflecting lens (50) response range is 380-780mm.
3. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that first photodetector (51), the second photodetector (52) are side window shape of the mouth as one speaks multialkali photoca PMT (1914F), TE refrigeration, spectral response range 190-860nm.
4. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that the sample cell (60) is the quartz colorimetric utensil of four sides light passing, outer dimension 12.5*12.5* 45mm, light path 10*10mm.
5. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that the optical filter (70) is BP700 bandpass filter, and central wavelength is 700nm, bandwidth 10nm, Half-peak band width is 45nm, to pass through 703nm Raman response signal.
6. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that the single photon counter (80) is SPCM-AQRH, and monitoring wave-length coverage is 400nm to 1060nm.
7. the dress that a kind of difference single photon Raman sensing according to claim 1 quick and precisely detects wheat vomitoxin It sets, which is characterized in that the data analysis and processing unit (54) is the voltage value of optical signal obtaining module 53 through overvoltage Collection plate is connected to the end PC, then carries out establishing least square model unit again.
8. the detection method that a kind of difference single photon Raman sensing quick and precisely detects wheat vomitoxin, which is characterized in that packet It includes following steps: 1) crushing the wheat of head blight, ethyl alcohol is added, be detected after ultrasound, centrifugation removal supernatant Liquid sample;2) golden stick Nano sol is concentrated, mixes, is put into sample cell (60) after addition NaCl;3) first laser device is opened (10), laser first passes through first laser collimator (30), then by semi-transparent semi-reflecting lens (50), anti-when by semi-transparent semi-reflecting lens (50) The light penetrated is perceived by the first photodetector (51), and the electric signal of output is converted using optical signal obtaining module (53) After export v1, the laser irradiation sample cell (60) of transmission excites its Raman response, and the Raman response that sample issues passes through optical filter (70) it after, is perceived by single photon counter (80), the current value of single photon counter (80) output passes through optical signal obtaining V ' is exported after module (53) conversionIt is single, close first laser device (10);4) second laser (20) are opened, step is first with 3) laser By second laser collimator (40), then by semi-transparent semi-reflecting lens (50), by the light that is reflected when semi-transparent semi-reflecting lens (50) by the Two photodetectors (52) perceive, and the electric signal of output exports v after converting using optical signal obtaining module (53)2, The laser irradiation sample cell (60) of transmission excites its Raman response, and the Raman response that sample issues is after optical filter (70), quilt Single photon counter (80) is perceived, and the current value of single photon counter (80) output turns by optical signal obtaining module (53) V " is exported after changingIt is single, close second laser (20), optical signal obtaining module exports v2、v″It is single;5) it utilizes and utilizes minimum two partially Multiply recurrence buildingThe dose-effect relationship of vomitoxin content in bivector and head blight wheat.
CN201910568001.9A 2019-06-27 2019-06-27 Device and method for detecting vomitoxin of wheat by differential single photon Raman Active CN110174393B (en)

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CN111504974A (en) * 2020-04-22 2020-08-07 安徽大学 Solution for vomitoxin detection, substrate preparation method and detection method
CN111521599A (en) * 2020-06-15 2020-08-11 中国海洋大学 Rapid detection system and detection method for micro-plastic in offshore sediments based on spatial heterodyne difference Raman spectroscopy

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CN111504974A (en) * 2020-04-22 2020-08-07 安徽大学 Solution for vomitoxin detection, substrate preparation method and detection method
CN111521599A (en) * 2020-06-15 2020-08-11 中国海洋大学 Rapid detection system and detection method for micro-plastic in offshore sediments based on spatial heterodyne difference Raman spectroscopy

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