CN100362338C - Method for acquiring optimal variable angle synchronous fluorescent spectrum - Google Patents
Method for acquiring optimal variable angle synchronous fluorescent spectrum Download PDFInfo
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- CN100362338C CN100362338C CNB2005100050069A CN200510005006A CN100362338C CN 100362338 C CN100362338 C CN 100362338C CN B2005100050069 A CNB2005100050069 A CN B2005100050069A CN 200510005006 A CN200510005006 A CN 200510005006A CN 100362338 C CN100362338 C CN 100362338C
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Abstract
The present invention relates to a method for obtaining optimal variable angle synchronous fluorescence spectra. First, isohypse projection drawings of three-dimensional fluorescence spectra are drawn by three-dimensional fluorescence spectrum data obtained through experiments; then, a scanning path is selected from the isohypse spectrum projection drawings; fluorescence intensity values of each data point in the selected path are obtained through interpolation on each data point by a two-dimensional cubic convolution interpolation method; next, a variable angle synchronous fluorescence spectrum corresponding to the selected path is drawn; finally, the scanning paths are repeatedly selected, and a plurality of corresponding variable angle synchronous fluorescence spectra are drawn, and the optimal variable angle synchronous fluorescence spectra and the optimal scanning paths can be obtained through comparing the selected scanning paths and the drawn variable angle synchronous fluorescence spectra. The required optimal spectra and the optimal scanning paths can be obtained through programming according to the method. The present invention experimentally and effectively provides the convenient and reliable reference for the qualitative and quantitative analysis on congener materials through fluorescence spectra, and also provides the reference standard for the design of variable angle synchronous fluorescence spectrographs.
Description
Technical field
A kind of method of utilizing the three-dimensional fluorescence spectrum data to obtain optimal variable angle synchronous fluorescent spectrum has also been determined optimum scanning pattern simultaneously.
Background technology
Fluorometry is an analytical technology that is widely used in every field such as industry, agricultural, medicine, health, judicial expertise and scientific research.Traditional fluorometry refers to the two dimension of utilizing material property fluorescence and launches (or exciting) spectrum carries out qualitative or quantitative test to material method.Compare with two dimension emission (or exciting) spectrum, fluorescence intensity is more with the quantity of information that the Three-Dimensional Fluorescence Spectra of excitation wavelength and variation in emission wavelength provides.Thereby utilize a kind of Validity Test method of the analytic approach of Three-Dimensional Fluorescence Spectra as research crude oil geochemistry characteristic, more and more be subject to people's attention.But obtaining the method for three-dimensional fluorescence data usually, is a series of emission spectrum that the continuous sweep emission wavelength obtains on different excitation wavelengths position, and the acquisition of a Three-Dimensional Fluorescence Spectra need be gathered tens two-dimentional emission spectrum usually, and is experimentally very time-consuming.The non-linear variable angle synchronous fluorescent spectrum that recent development is got up (Variable-angle synchronous fluorescence spectrum) is a kind of fluorometry of new high selectivity, and the various features that it can will be expressed three-dimensional collection of illustrative plates show with special two-dimensional map pattern and receive much concern.In theory, variable angle synchronous fluorescent spectrum (VASFS) just can obtain the information that deviser's expectation obtains from a Three-Dimensional Fluorescence Spectra by suboptimum scanning.This technical requirement wavelength of transmitted light and excitation wavelength are by certain scanning pattern synchronous scanning of design, and its key is to find optimum scanning pattern.Wherein, choosing of optimum path should consider to try one's best few spectra overlapping simultaneously according to the requirement of analyzing, and approaches the maximum fluorescence intensity value of each component most, and the interference of avoiding scattering as much as possible.
Given this, at present when utilizing the variable angle synchronous fluorimetry to analyze multi-component material, usually design along the variable angle synchronous fluorescent spectrum instrument of specific scanning pattern scanning according to the needs of particular analysis at predetermined substance, and this scanning pattern promptly is to satisfy to analyze the optimum path that requires, adopt comparatively blindly method of trial and error to test to obtain and this scanning pattern at present more, not only time-consuming, and be subjected to the restriction of the factors such as subjective experience of instrument performance and testing crew, influenced the quality of variable angle synchronous fluorescent spectrum so greatly with regard to having limited choosing of optimum path to a great extent, this test method implements also very time-consuming simultaneously.If on fluorescence spectrophotometer, measure multiple inhomogeneous material simultaneously, then need each class material is determined its corresponding optimum path, with regard to complicated more and time-consuming, limited promoting the use of of fluorescence spectrophotometer to a certain extent like this.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, a kind of method of obtaining optimal variable angle synchronous fluorescent spectrum quickly and easily is provided, also determined simultaneously optimum scanning pattern, so that by the fluorescence spectrum that obtains material is carried out fully effectively qualitative and quantitative analysis, and saving must this spectrogram is obtained in a large amount of experiments and optimum path is needed expends by doing greatly.
Another object of the present invention is the design for the variable angle fluorescence spectrophotometer, and promptly the predetermined substance that needs are measured can provide optimum path, makes it measure the optimal variable angle synchronous fluorescent spectrum of respective substance easily and fast.
Method of the present invention or step: at first read experimentally acquired three-dimensional fluorescence spectrum data, and draw out the level line perspective view of three-dimensional fluorescence spectrum, in level line spectrum projection figure, select the zigzag scanning path then and read this scanning pattern, pass through interpolation method, each data point in the selected zigzag scanning path is carried out interpolation obtain the corresponding fluorescence intensity level of these points, and then draw out a variable angle synchronous fluorescent spectrum figure of selected zigzag scanning path correspondence, again by selecting the zigzag scanning path repeatedly and drawing out many variable angle synchronous fluorescent spectrum figure accordingly, according to the requirement of analyzing, and few spectra overlapping of considering to try one's best, come more resulting each fluorescence spectrum figure with the maximum fluorescence intensity value that approaches each component, can obtain optimum variable angle synchronous fluorescent spectrum figure (VASFS), and the corresponding scanning pattern of this fluorescence spectrum is defined as the optimum path of the satisfied analysis needs of this material.Usually only need select the 3-5 bar can obtain variable angle synchronous fluorescent spectrum figure repeatedly.
Above-mentioned interpolation method can be taked multiple, as bilinear interpolation or two cubes of Hermite interpolation, the present invention considers that the fluorescence intensity curved surface after the interpolation need be consistent with reality in the bending at place, site, chosen two-dimentional cubic convolution interpolation method so that obtain optimized collection of illustrative plates and the three-dimensional fluorescence spectrum data are carried out local interpolation obtained interpolating function, obtained the fluorescence intensity level of each data point in the selected scanning pattern with this.The interpolating function that interpolation method of the present invention obtains is that three times of three-dimensional fluorescence spectrum curved surface approach, and has three continuous order derivatives, can well satisfy the needs that variable angle synchronous fluorescent spectrum obtains.
In program composition, it is also conceivable that when in level line spectrum projection figure, selecting the zigzag scanning path, so that three-dimensional fluorescence spectrum there is the impression intuitively of an integral body.The present invention can draw out three-dimensional fluorescence spectrum figure and three-dimensional level line spectrogram in drawing three-dimensional fluorescence spectrum level line perspective view after reading the three-dimensional fluorescence spectrum data.Promptly after reading the three-dimensional fluorescence spectrum data, in drawing three-dimensional fluorescence spectrum level line perspective view, on the interface, draw out three-dimensional fluorescence spectrum figure and three-dimensional level line spectrogram.
Can work out out the program of obtaining optimal variable angle synchronous fluorescent spectrum and optimum path according to above-mentioned steps, and realize that according to this demonstration of multiple fluorescence spectrum figure and various operation are to carry out intuitive analysis to spectrum, this optimum path also just provides optimum path for fluorescence spectrophotometer designs this material of mensuration, simultaneously also provide normative reference, to realize the convenient optimal variable angle synchronous fluorescent spectrum of measuring respective substance for the design of the variable angle synchronous fluorescent spectrum figure that measures predetermined substance.
Description of drawings
Fig. 1 is a program flow diagram of the present invention.
Fig. 2 is the level line spectrum projection figure (wherein having selected three zigzag scanning paths) that utilizes the three-dimensional fluorescence spectrum of three-dimensional fluorescence spectrum data drafting.Asterism is represented the reference mark in zigzag scanning path among the figure, and the dotted line that connects asterism is represented the zigzag scanning path.Wherein thicker one is optimum path, and two other is non-optimum path.
Fig. 3 be with Fig. 2 in three variable angle synchronous fluorescent spectrum figure that the zigzag scanning path is corresponding.Asterism among the figure in the circle corresponding diagram 2 zigzag scanning paths.Wherein thicker one is optimal variable angle synchronous fluorescent spectrum, and two other is non-optimal variable angle synchronous fluorescent spectrum.The coordinate that has one group of coordinate (371.7566,380.035) to give directions among the figure for arrow, wherein horizontal ordinate is represented the wavelength of transmitted light of this point, ordinate is represented the fluorescence intensity level of the corresponding point position under this wavelength of transmitted light in the selected scanning pattern.
Fig. 4 a is the level line spectrum projection figure that contains a scanning pattern.
Fig. 4 b is the variable angle synchronous fluorescent spectrum figure that matches under the scanning pattern among Fig. 4 a of experiment and the present invention's acquisition.
Fig. 5 is the program master interface of the variable angle synchronous fluorescent spectrum figure under two scanning patterns of the present invention's drafting.Demonstrated among the level line perspective view (lower-left) of three-dimensional fluorescence spectrum figure (upper left), three-dimensional level line spectrogram (upper right), three-dimensional fluorescence spectrum and the level line spectrum projection figure variable angle synchronous fluorescent spectrum figure (bottom right) under two scanning patterns in the interface simultaneously.
Embodiment
The present invention at first reads experimentally acquired three-dimensional fluorescence spectrum data, and draw out the level line perspective view of three-dimensional fluorescence spectrum, in level line spectrum projection figure, select the zigzag scanning path then and read this scanning pattern, pass through interpolation method, each data point in the selected zigzag scanning path is carried out interpolation obtain the corresponding fluorescence intensity level of these points, and then draw out a variable angle synchronous fluorescent spectrum figure of selected zigzag scanning path correspondence, again by selecting the zigzag scanning path repeatedly and drawing out many variable angle synchronous fluorescent spectrum figure accordingly, more resulting each fluorescence spectrum figure, can obtain optimum variable angle synchronous fluorescent spectrum figure, and the corresponding scanning pattern of this fluorescence spectrum is defined as the optimum path of the satisfied analysis needs of this material.
The present invention has chosen two-dimentional cubic convolution interpolation method and the three-dimensional fluorescence spectrum data are carried out local interpolation has obtained interpolating function, obtains the fluorescence intensity level of each data point in the selected scanning pattern with this.
Consider when in level line spectrum projection figure, selecting the zigzag scanning path, be convenient to three-dimensional fluorescence spectrum is had the impression intuitively of an integral body.The present invention can draw out three-dimensional fluorescence spectrum figure and three-dimensional level line spectrogram in drawing three-dimensional fluorescence spectrum level line perspective view after reading the three-dimensional fluorescence spectrum data.Promptly after reading the three-dimensional fluorescence spectrum data, in drawing three-dimensional fluorescence spectrum level line perspective view, on the interface, draw out three-dimensional fluorescence spectrum figure and three-dimensional level line spectrogram.Concrete steps are as follows:
1. read and store experimentally acquired three-dimensional fluorescence spectrum data (the three-dimensional fluorescence spectrum data are that the form with grid provides the fluorescence intensity information on the net point), and utilize the three-dimensional fluorescence spectrum data to draw out three-dimensional fluorescence spectrum figure, three-dimensional level line spectrogram and level line spectrum projection figure (Fig. 2) simultaneously.Wherein three-dimensional fluorescence spectrum and level line spectrogram have demonstrated the Global Information of fluorescence data intuitively, and level line spectrum projection figure then is used for selecting each zigzag scanning path.
2. in level line spectrum projection figure, select zigzag scanning path (as shown in phantom in Figure 2), the zigzag scanning path is controlled by the reference mark, finish the choosing of scanning pattern by choosing each reference mark in the scanning pattern, these scanning patterns are made up of with the dotted line that is connected asterism the asterism among the figure.
3. selected scanning pattern in reading 2. promptly reads each the asterism coordinate in the scanning pattern when selecting scanning pattern, and connects each asterism formation zigzag scanning path successively.
2., 3. in coding be implemented among the level line spectrum projection figure when selecting scanning pattern as the scanning pattern reference mark with asterism, can in level line spectrum projection figure, utilize left mouse button to click the reference mark of selected scanning pattern, store these reference mark, and the form of these reference mark with asterism be presented among the level line spectrum projection figure, with dashed lines connects each reference mark (asterism) successively and represents selected scanning pattern simultaneously.
The variable angle synchronous fluorescent spectrum figure of the zigzag scanning path correspondence that reads in 4. drawing 3., promptly utilize two-dimentional cubic convolution interpolation method that each data point in the zigzag scanning path of reading in is 3. carried out interpolation, obtain the fluorescence intensity level at each data point place on this zigzag scanning path, can utilize two-dimentional mapping function to draw out the corresponding variable angle synchronous fluorescent spectrum figure in this zigzag scanning path.
Above-mentioned interpolation is if when utilizing general mathematics manipulation software Matlab to finish, and this two-dimentional cubic convolution interpolation method is called the Cubic interpolation three times, wherein by I=interp2 (X, Y, Z, xxi, yyi, ' cubic '); Order obtains interpolation result, in this order, and X, Y, Z are original three-dimensional fluorescence spectrum grid data, and xxi, yyi are horizontal stroke, the ordinate value of required interpolation point, ' cubic ' represents interpolation type, interpolation result I is interpolation point (xxi, the fluorescence intensity level of yyi) locating.
5. 2., 3., 4. select a zigzag scanning path again and read this path by above-mentioned steps, obtain the variable angle synchronous fluorescent spectrum figure of this scanning pattern correspondence simultaneously.
6. more 4., two variable angle synchronous fluorescent spectrum figure obtaining in 5., and therefrom select to reflect of fluorescence spectrum information to see whether satisfy the needs of analyzing, whether be optimum variable angle synchronous fluorescent spectrum figure promptly.If 4., two variable angle synchronous fluorescent spectrum figure that obtain in 5. all can not satisfy the demand, can repeat step 5., the variable angle synchronous fluorescent spectrum figure that continues to select next bar zigzag scanning path and obtain this scanning pattern correspondence, see whether satisfy the demand, till obtaining optimum variable angle synchronous fluorescent spectrum figure, the scanning pattern of this fluorescence spectrum correspondence is optimum path, and detailed program circuit as shown in Figure 1.
Three different zigzag scannings paths for having selected among Fig. 2, Fig. 3 is the variable angle synchronous fluorescent spectrum figure under each scanning pattern among Fig. 2.More as can be seen, thicker one is optimal variable angle synchronous fluorescent spectrum to the variable angle synchronous fluorescent spectrum figure among Fig. 3, and zigzag scanning path thicker among Fig. 2 corresponding with it is optimum path.
In Fig. 4 b, be example with many components oil sample of representative complexity, the variable angle synchronous fluorescent spectrum figure under the scanning pattern shown in Fig. 4 a of obtaining of utilization experiment and two kinds of methods of the present invention respectively.As can be seen from the figure, two kinds of variable angle synchronous fluorescent spectrum figure basically identicals that method obtains in error range, through the too much test of group experimental data, all drawn identical result, further verified and utilized the three-dimensional fluorescence spectrum data, the reliability of the variable angle synchronous fluorescent spectrum that obtains by method of the present invention.
Fig. 5 be by general mathematics manipulation software Matlab by the present invention programme the program master interface that obtains and on four width of cloth spectrograms.The analyst utilizes this program can demonstrate the level line perspective view of three-dimensional fluorescence spectrum figure, three-dimensional level line spectrogram and three-dimensional fluorescence spectrum simultaneously in same interface.So just can select optimum zigzag scanning path at the level line perspective view according to the requirement of analyzing intuitively, and obtain optimum variable angle synchronous fluorescent spectrum figure.In addition, can also use other programming languages (as Vc) to realize each step among the present invention.
Can obtain the optimal variable angle synchronous fluorescent spectrum of needs by written program of the present invention, and determine optimum path simultaneously, convenience and reliable basis are provided for experimentally by fluorescence spectrum allied substances being carried out qualitative and quantitative analysis most effectively, also having saved greatly in the past must this spectrogram is obtained in a large amount of experiments and optimum path is needed expends by doing, and obviously the design to the variable angle synchronous fluorescent spectrum instrument of predetermined substance provides foundation.
Claims (2)
1. method of obtaining optimal variable angle synchronous fluorescent spectrum, it is characterized in that it is to utilize experimentally acquired three-dimensional fluorescence spectrum data to draw out the level line perspective view of three-dimensional fluorescence spectrum, in level line spectrum projection figure, select the zigzag scanning path then and read this scanning pattern, by interpolation method each data point in the selected zigzag scanning path is carried out interpolation and obtain the corresponding fluorescence intensity level of these points, promptly using two-dimentional cubic convolution interpolation algorithm that the three-dimensional fluorescence spectrum data are carried out local interpolation obtains three times and approaches interpolating function, and obtain the fluorescence intensity level of each data point in the selected scanning pattern with this, and then draw out a variable angle synchronous fluorescent spectrum figure of selected zigzag scanning path correspondence, again by selecting the zigzag scanning path repeatedly and drawing out many variable angle synchronous fluorescent spectrum figure accordingly, more resulting each fluorescence spectrum figure, can obtain optimum variable angle synchronous fluorescent spectrum figure, and the corresponding scanning pattern of this fluorescence spectrum is defined as the optimum path of the satisfied analysis needs of this material.
2. the method for obtaining optimal variable angle synchronous fluorescent spectrum as claimed in claim 1, it is characterized in that above-mentionedly after reading the three-dimensional fluorescence spectrum data, in drawing three-dimensional fluorescence spectrum level line perspective view, on the interface, draw out three-dimensional fluorescence spectrum figure and three-dimensional level line spectrogram.
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| CN102998294B (en) * | 2012-12-20 | 2014-10-22 | 中国环境科学研究院 | Three-dimensional spectroscopic data correction method |
| CN107367494A (en) * | 2017-07-13 | 2017-11-21 | 上海交通大学 | The method for distinguishing recombined milk and fresh milk is detected with endogenous fluorescence spectral technique |
| CN110836878B (en) * | 2019-11-01 | 2021-09-07 | 同济大学 | Convolution interpolation coupling Gaussian mixture model rapid three-dimensional fluorescence peak searching method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4293221A (en) * | 1979-04-17 | 1981-10-06 | Research Corporation | Multidimensional slit-scan flow system |
| CN1397813A (en) * | 2002-08-30 | 2003-02-19 | 清华大学 | Process for preparing high-chip optical fibre raster with controllable transmission (reflection) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4293221A (en) * | 1979-04-17 | 1981-10-06 | Research Corporation | Multidimensional slit-scan flow system |
| CN1397813A (en) * | 2002-08-30 | 2003-02-19 | 清华大学 | Process for preparing high-chip optical fibre raster with controllable transmission (reflection) |
Non-Patent Citations (5)
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| FTOTAL,,A PROGRAM TO PROCESSTOTAL LUMINESCENCE SPECTRA. J.A.Murillo Pulgarin et al.Computers Chem.,Vol.17 No.4. 1993 * |
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