CN104237199A - Raman detection system and Raman detection method based on diffusion mode - Google Patents
Raman detection system and Raman detection method based on diffusion mode Download PDFInfo
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- CN104237199A CN104237199A CN201410432576.5A CN201410432576A CN104237199A CN 104237199 A CN104237199 A CN 104237199A CN 201410432576 A CN201410432576 A CN 201410432576A CN 104237199 A CN104237199 A CN 104237199A
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Abstract
The invention provides a Raman detection system and a Raman detection method based on a diffusion mode. The system comprises multiple laser point light sources, a two-dimensional translation sample stage, a lens, a Raman spectrometer, a CCD and a processor, wherein the multiple laser point light sources are used for simultaneously emitting dotted laser and allowing the dotted laser to irradiate to different positions of samples arranged on the two-dimensional translation sample stage; the two-dimensional translation sample stage is used for allowing the samples to move in the two-dimensional direction during detection; the lens is used for collecting diffusion signal light emitted by all the dotted laser passing through the samples; the Raman spectrometer is used for receiving the diffusion signal light to acquire a light signal; the CCD is used for converting the light signal into an electric signal and acquiring a Raman diffusion image of the samples; and the processor is used for analyzing the samples according to the Raman diffusion image of the sample. According to the system and the method disclosed by the invention, the detection efficiency and the detection accuracy are improved, and the system and the method have high application values.
Description
Technical field
The present invention relates to detection technique field, particularly relate to a kind of Raman detection system based on diffusion way and method.
Background technology
Along with the abuse of development in science and technology and chemicals, food security is becoming the problem of countries in the world growing interest.In the last few years, in succession there are the illegal incidents that many cases food security causes in China.Some contraband goodss or fake and forged product, in order to seek exorbitant profit, are added in agricultural and animal products and food by some lawless persons, and the health of use to consumer of these illegal additives causes serious injury.Therefore, in order to early warning with analyze the harm of illegal additive and prevent the generation of this type of food safety affair, accurately detect and analyze illegal additive in food and seem particularly important.
In the standard detecting method of prior art, sample pre-treatments needs long time usually, cannot reach the object detected fast.Lossless manner how can be utilized to carry out sample detect fast, thus wherein content of material is measured and Qualitive test, become an important topic.
Summary of the invention
The invention provides a kind of Raman detection system based on diffusion way and method, to realize detecting fast the harmless of sample.
First a kind of Raman detection system based on diffusion way of the present invention, comprising: multiple laser point light source, two-dimension translational sample stage, camera lens, Raman spectrometer, CCD and processor; Wherein:
Described multiple laser point light source is used for launching point-like laser simultaneously, and makes described point laser irradiation on the diverse location of sample being placed in described two-dimension translational sample stage;
When described two-dimension translational sample stage is for detecting, described sample is moved at two-dimensional directional;
Described camera lens is for collecting the diffusion signal light of all point-like lasers through described sample outgoing;
Described Raman spectrometer, for receiving described diffusion signal light, obtains light signal;
Described CCD is used for described light signal to be converted to electric signal, obtains the Raman diffusion image of described sample;
Described processor is used for analyzing described sample according to the Raman diffusion image of described sample.
Further, the number of described laser point light source is 3.
Further,
Described multiple laser point light source is 785nm laser point light source.
Further, described system also comprises:
785nm cutoff filter, between described two-dimension translational sample stage and described camera lens, for carrying out light cutoff filter to the diffusion signal light through described sample outgoing, retains the diffusion signal light that wavelength is more than 785nm.
Further,
Described laser point light source makes described point laser irradiation on sample through optical fiber and adapter.
Further,
The described laser point light source spot diameter be irradiated on sample is 1mm.
Further,
Described Raman spectrometer also comprises slit, and described Raman spectrometer is used for collecting described diffusion signal light by described slit;
Described multiple laser point light source is parallel to described slit direction, arrangement in alignment, and ensure that described laser point light source is irradiated to the diffusion signal light of outgoing on sample can through described slit collected by described Raman spectrometer.
Further, being spaced apart between described multiple laser point light source is identical or different.
On the other hand, the present invention also provides a kind of Raman detection method based on diffusion way, utilizes the Raman detection system based on diffusion way as above described in any one to detect, comprising:
Step S1: make multiple point laser irradiation on the diverse location of sample being placed in two-dimension translational sample stage;
Step S2: collect the diffusion signal light of all point-like lasers through described sample outgoing;
Step S3: receive described diffusion signal light, obtain light signal;
Step S4: described light signal is converted to electric signal, obtains the Raman diffusion image of described sample;
Step S5: by described sample by described two-dimension translational sample stage in two-dimensional directional translation, and constantly repeat above-mentioned steps S1-S4, obtain many group Raman diffusion images;
Step S6: described sample is analyzed according to described Raman diffusion image.
Further, described step S6 also comprises:
Being averaged to often organizing Raman diffusion image, obtaining average diffusion image Y
i:
Y
i＝(Y
i1+Y
i2+……+Y
im)/m (i＝1,2,……，n)，
Wherein n is the number of Raman diffusion image group; M is the number of laser point light source;
To described average diffusion image Y
icarry out Mathematical Fitting analysis, obtain described average diffusion image Y
ithe content of material distribution of corresponding sample position;
And/or, to all average diffusion image Y
ibe averaged, obtain the average diffusion image Y of described sample, according to the average diffusion image Y of described sample the qualitative of content of material carried out to described sample and/or quantitatively differentiate.
Visible, in the Raman detection system based on diffusion way provided by the invention and method, Raman can be utilized to spread the mode detected Fast nondestructive evaluation is carried out to content of material and distribution, improve efficiency and the accuracy of detection, there is higher using value.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation based on the Raman detection system of diffusion way in one embodiment of the present of invention;
Fig. 2 is based on the Raman detection system of diffusion way preferred structure schematic diagram in one embodiment of the present of invention;
Fig. 3 is based on the Raman detection system of diffusion way preferred structure schematic diagram in one embodiment of the present of invention;
Fig. 4 is the schematic flow sheet based on the Raman detection method of diffusion way in one embodiment of the present of invention;
Fig. 5 is the embody rule scene schematic diagram based on the Raman detection method of diffusion way in one embodiment of the present of invention;
Fig. 6 is Lorentz distribution function schematic diagram.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Fig. 1 shows a kind of structural representation of the Raman detection system based on diffusion way, and as shown in Figure 1, the present embodiment specifically comprises:
Multiple laser point light source 1, two-dimension translational sample stage 2, camera lens 3, Raman spectrometer 4, CCD5 and processor 6; Wherein:
Described multiple laser point light source 1 for launching point-like laser simultaneously, and makes described point laser irradiation on the diverse location of sample 7 being placed in described two-dimension translational sample stage 2;
Described sample 7 is made to move at two-dimensional directional when described two-dimension translational sample stage 2 is for detecting;
3, described mirror is for collecting the diffusion signal light of all point-like lasers through the outgoing of described sample 7;
Described Raman spectrometer 4, for receiving described diffusion signal light, obtains light signal;
Described CCD5 is used for described light signal to be converted to electric signal, obtains the Raman diffusion image of described sample 7;
Described processor 6 is analyzed described sample 7 for the Raman diffusion image according to described sample.
Alternatively, the number of laser point light source 1 can be 3, technically to obtain perfect measurement data most possibly at practice every conceivable frugality power consumption and measuring system volume.
Alternatively, laser point light source 1 can be 785nm laser point light source.
Correspondingly, can also comprise in system: 785nm cutoff filter 8, as shown in Figure 2, between two-dimension translational sample stage 2 and camera lens 3, for carrying out light cutoff filter to the diffusion signal light through sample 7 outgoing, only retain the diffusion signal light that wavelength is more than 785nm, thus make measuring-signal more accurate.
Alternatively, laser point light source 1 can all make point laser irradiation on sample 7 through optical fiber and adapter 9 (see Fig. 2).
The scope of the hot spot that laser point light source 1 is irradiated on sample 7 needs appropriateness, to avoid laser scattering on a large scale to make collected measuring-signal not enough, can obtain again diffusion signal light in a big way to a certain extent.Alternatively, laser point light source 1 is irradiated to the spot diameter on sample 7 can be 1mm.
Because the present embodiment adopts two-dimension translational sample stage 2 to carry out mobile example 7, therefore, alternatively, in testing process, Raman diffusion signal can be gathered with connecing a line by form line of line sweep, thus obtain the whole two dimensional image of sample 7.Wherein, Raman spectrometer 4 can also comprise slit 10, and as shown in Figure 3,11 is the projected position of slit 10 (not shown) on sample 7 on Raman spectrometer 4, and three arrows are depicted as the projected position of three laser point light sources 1 on sample.Raman spectrometer 4 can collect diffusion signal light by slit 10.Correspondingly, multiple laser point light source 1 can in straight line to be parallel to the direction arrangement of slit 10, diffusion signal light through sample outgoing is entered just by the slit of Raman spectrometer 4, thus the Raman scattered light signal obtained on a line, and be converted to sample Raman diffusion image on one wire through the AD signal of CCD5.
Fig. 2 shows a kind of Raman detection method based on diffusion way, utilizes the Raman detection system based on diffusion way as above described in any one to detect.See Fig. 4, the method in the present embodiment specifically comprises:
Step S1: make multiple point laser irradiation on the diverse location of sample being placed in two-dimension translational sample stage.
As shown in Figure 5, in an application scenarios of the present embodiment, pick-up unit comprises three laser point light sources 1, and parallel with the slit 10 on Raman spectrometer 4, arranges in straight line.First sample 7 being placed on two-dimension translational sample stage 2, making two-dimension translational sample stage 2 move from right to left along the x direction in figure, when moving to the Y of sample
1during place, the slit 10 of Raman spectrometer 4 just in time aims at Y
1, three laser point light sources 1 through Optical Fiber Transmission, and through adapter 9 change point-like laser parallel radiation to Y
1y on sweep trace
11, Y
12and Y
13place.
Step S2: collect the diffusion signal light of all point-like lasers through described sample outgoing.
Particularly, at the Y of above-mentioned scene
1y on sweep trace
11, Y
12and Y
13place, can form the hot spot that diameter is the non-overlapping copies of 1mm respectively, collects the diffusion signal light of all hot spot outgoing from sample surfaces diffusion.
Step S3: receive described diffusion signal light, obtain light signal.
Step S4: described light signal is converted to electric signal, obtains the Raman diffusion image of described sample.
Step S5: by described sample by described two-dimension translational sample stage in two-dimensional directional translation, and constantly repeat above-mentioned steps S1-S4, obtain many group Raman diffusion images.
Particularly, in the scene involved by step S1 and step S2, can Y in Figure 5
2, Y
3above-mentioned S1-S4 step is repeated respectively at place, thus at every bar sweep trace Y
iplace obtains the Raman diffusion image of this sweep trace.
Step S6: described sample is analyzed according to described Raman diffusion image.
Particularly, step S6 can also comprise: being averaged to often organizing Raman diffusion image, obtaining average diffusion image Y
i:
Y
i＝(Y
i1+Y
i2+……+Y
im)/m (i＝1,2,……，n)，
Wherein n is the number of Raman diffusion image group, also namely utilizes the number of times of step S1-S4 duplicate detection; M is the number of laser point light source.
To described average diffusion image Y
icarry out Mathematical Fitting analysis, obtain average diffusion image Y
ithe content of material distribution of corresponding sample position.
Or, can also to all average diffusion image Y
ibe averaged, obtain the average diffusion image Y of described sample, according to the average diffusion image Y of described sample the qualitative of content of material carried out to described sample and/or quantitatively differentiate.
Such as in an application scenarios of the present embodiment, can utilize the space diffusion profile at each wavelength place of Lorentz distribution function matching average diffusion image Y, Fig. 6 is shown in by Lorentz distribution function schematic diagram.Following formula (1) is Lorentz three parameter fitting mathematical expression:
Wherein, R is the reflection strength (CCD gray-scale value) of any point on scattering curve; Z is the distance of diffusion profile decentering point, unit mm; A is the asymptotic value of diffusion profile; C is the half-wave bandwidth of diffusion profile at the b/2 place of peak value, unit mm; B is the peak value of diffusion profile at sweep trace central point x=0 place.
At beam area-98 ~ 3998cm of spectrum
-1in (corresponding wavelength scope 799 ~ 1144nm), Lorentzian can be utilized to carry out matching at each wavelength place.
Particularly, in MATLAB, nonlinear partial autocorrelation iunction for curve lsqcurvefit () can be utilized to realize three parameter fittings of Lorentzian at each wavelength place.Total number of samples is divided into two groups by 3:1 at random, and calibration set accounts for 3/4 of population sample, and forecast set accounts for 1/4 of population sample.The Lorentz three parameter a obtained through Lorentzian matching, b, c combine, Lorentz three parameter combinations matrix A ([abc]) is used to set up partial least-squares regression method (partial least squares regression, PLSR) forecast model.If three of Lorentzian parameters matrix is separately a (n × m), b (n × m), c (n × m), wherein n is sample number, and m is Effective wave number, then Lorentz three parameter combinations matrix A is n × 3m combinatorial matrix, wherein, front m row are Lorentz parameter a, and middle m row are Lorentz parameter b, and rear m row are Lorentz parameter c.The characteristic spectrum information of Lorentz three parameter combinations A representative sample participates in the foundation of Q factor forecast model.
Wherein partial least squares regression (PLSR) model formation is:
Y＝XB+E (2)
Y＝AB+E (3)
In formula, Y is the chemical score matrix measured with standard method, and X is the spectrum parameter matrix of body surface dispersion image, and A is three parameter matrixs of matching, and E is constant term matrix.Formula (2) is the linear model mathematical expression of conventional partial least squares regression, and formula (3) is for replace spectrum parameter matrix X to set up Partial Least-Squares Regression Model with three parameter matrix A of matching.
Therefore, in the present invention in the Raman detection system based on diffusion way that provides of embodiment and method, Raman can be utilized to spread the mode detected Fast nondestructive evaluation is carried out to content of material and distribution, improve efficiency and the accuracy of detection, there is higher using value.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. based on a Raman detection system for diffusion way, it is characterized in that, comprising: multiple laser point light source, two-dimension translational sample stage, camera lens, Raman spectrometer, CCD and processor; Wherein:
Described multiple laser point light source is used for launching point-like laser simultaneously, and makes described point laser irradiation on the diverse location of sample being placed in described two-dimension translational sample stage;
When described two-dimension translational sample stage is for detecting, described sample is moved at two-dimensional directional;
Described camera lens is for collecting the diffusion signal light of all point-like lasers through described sample outgoing;
Described Raman spectrometer, for receiving described diffusion signal light, obtains light signal;
Described CCD is used for described light signal to be converted to electric signal, obtains the Raman diffusion image of described sample;
Described processor is used for analyzing described sample according to the Raman diffusion image of described sample.
2. the Raman detection system based on diffusion way according to claim 1, is characterized in that: the number of described laser point light source is 3.
3., according to the Raman detection system based on diffusion way according to claim 1, it is characterized in that:
Described multiple laser point light source is 785nm laser point light source.
4. the Raman detection system based on diffusion way according to claim 3, is characterized in that, described system also comprises:
785nm cutoff filter, between described two-dimension translational sample stage and described camera lens, for carrying out light cutoff filter to the diffusion signal light through described sample outgoing, retains the diffusion signal light that wavelength is more than 785nm.
5. the Raman detection system based on diffusion way according to claim 1, is characterized in that:
Described laser point light source makes described point laser irradiation on sample through optical fiber and adapter.
6. the Raman detection system based on diffusion way according to claim 1, is characterized in that:
The described laser point light source spot diameter be irradiated on sample is 1mm.
7. the Raman detection system based on diffusion way according to claim 1, is characterized in that:
Described Raman spectrometer also comprises slit, and described Raman spectrometer is used for collecting described diffusion signal light by described slit;
Described multiple laser point light source is parallel to described slit direction, arrangement in alignment, and ensure that described laser point light source is irradiated to the diffusion signal light of outgoing on sample can through described slit collected by described Raman spectrometer.
8. the Raman detection system based on diffusion way according to any one of claim 1 to 7, is characterized in that:
Being spaced apart between described multiple laser point light source is identical or different.
9. based on a Raman detection method for diffusion way, it is characterized in that, utilize the Raman detection system based on diffusion way according to any one of claim 1 to 8 to detect, comprising:
Step S1: make multiple point laser irradiation on the diverse location of sample being placed in two-dimension translational sample stage;
Step S2: collect the diffusion signal light of all point-like lasers through described sample outgoing;
Step S3: receive described diffusion signal light, obtain light signal;
Step S4: described light signal is converted to electric signal, obtains the Raman diffusion image of described sample;
Step S5: by described sample by described two-dimension translational sample stage in two-dimensional directional translation, and constantly repeat above-mentioned steps S1-S4, obtain many group Raman diffusion images;
Step S6: described sample is analyzed according to described Raman diffusion image.
10. the Raman detection method based on diffusion way according to claim 9, it is characterized in that, described step S6 also comprises:
Being averaged to often organizing Raman diffusion image, obtaining average diffusion image Yi:
Y
i＝(Y
i1+Y
i2+……+Y
im)/m (i＝1,2,……，n)，
Wherein n is the number of Raman diffusion image group; M is the number of laser point light source;
To described average diffusion image Y
icarry out Mathematical Fitting analysis, obtain described average diffusion image Y
ithe content of material distribution of corresponding sample position;
And/or, to all average diffusion image Y
ibe averaged, obtain the average diffusion image Y of described sample, according to the average diffusion image Y of described sample the qualitative of content of material carried out to described sample and/or quantitatively differentiate.
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