CN105699356A - Method for judging fluorescence quenching degree of Raman spectrum through information entropy - Google Patents

Method for judging fluorescence quenching degree of Raman spectrum through information entropy Download PDF

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CN105699356A
CN105699356A CN 201610093394 CN201610093394A CN105699356A CN 105699356 A CN105699356 A CN 105699356A CN 201610093394 CN201610093394 CN 201610093394 CN 201610093394 A CN201610093394 A CN 201610093394A CN 105699356 A CN105699356 A CN 105699356A
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fluorescence
method
entropy
information
raman
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CN 201610093394
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Chinese (zh)
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姚志湘
粟晖
刘柳
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广西科技大学
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    • GPHYSICS
    • 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 infra-red, visible or ultra-violet 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

Abstract

The invention discloses a method for judging the fluorescence quenching degree of Raman spectrum through information entropy and relates to a Raman spectrum fluorescence quenching method. The method uses the discrete-sequence information entropy as the criterion of fluorescence deduction, fluorescence is gradually deducted from a mixed signal, and the fluorescence in the mixed signal is completely quenched when the information entropy reaches the minimum. The method has the advantages that the fluorescence quenching degree is judged through the information entropy, the method is scientific and reasonable and unlimited by instrument wave-number range, instrument performance can be brought into full play, and the freedom degree of instrument design and manufacturing is increased; the limitation that the fluorescence residue situation needs to be judged in a specific wavelength range in the prior art is solved, no special requirement on spectrum range is needed, and the method is adaptive to instrument design with different wavelength settings; Raman true signals which conform to actual mechanisms and are not interfered by fluorescence can be obtained fast and accurately while equipment complexity is not increased and an existing measuring habit is not changed, and the method is easy to popularize and use.

Description

通过信息熵判断拉曼光谱的荧光消除程度的方法 Elimination of fluorescence degree is determined by Raman spectroscopy method of entropy

技术领域 FIELD

[0001] 本发明涉及一种拉曼光谱荧光消除方法,特别是一种通过信息熵判断拉曼光谱的荧光消除程度的方法。 [0001] The present invention relates to a method for eliminating the Raman spectrum fluorescent, in particular a fluorescence Raman spectrum determining the extent eliminated by the method of information entropy.

背景技术 Background technique

[0002] 激光拉曼光谱可以提供分子光谱信息,同时具有不容易被水分干扰、非接触和不破坏样品等优点,是一种快速发展的定性定量分析手段。 [0002] Raman spectroscopy can provide information on molecular spectroscopy, moisture interference while having the advantage of non-contact and non-destructive to sample is not easy, qualitative and quantitative analysis is a means of rapid development. 但是,拉曼散射激发的同时产生的荧光,对拉曼光谱可辨识性和信号质量产生干扰。 However, while fluorescence excitation Raman scattering, Raman spectroscopy can interfere with identification and signal quality.

[0003] 采用阵列感光的微型分光式拉曼光谱仪近年来发展很快,优点是结构简单、无需复杂维护,但其采用硬件消除荧光干扰会增加设备的复杂程度,例如,利用拉曼光的迀移性和荧光的相对稳定,通过双波长激发消除荧光,仪器造价和复杂性都会提升。 [0003] The array of photosensitive spectroscopic micro Raman spectrometer developed rapidly in recent years, the advantages of simple structure, without complex maintenance, but its hardware to eliminate fluorescence interference will increase the complexity of the device, e.g., Raman light Gan shift relatively stable and fluorescence by the double excitation wavelength eliminate fluorescence, equipment cost and complexity are increased. 基线拟合扣减是目前此类拉曼光谱仪消荧光的主要思路,多数方法采用光谱基线拟合,扣减至初始位置, 给出荧光消除表象,实际无法从机理或实质上解释,结果既不真实也不合理。 Baseline fitting deduction is currently the main idea of ​​such Raman spectroscopy fluorescence extinction, most of the approaches adopted to fit the spectrum baseline, reduced to an initial position, eliminating fluorescence gives the appearance, or substantially the actual mechanism can not explain the result, neither real unreasonable.

[0004] 另有技术采用强光照射下荧光强度逐步降低的褪色效应,荧光强度整体下降,此部分度量反映了信号中的荧光特性,并从信号中逐步扣除,最终消除拉曼信号的荧光干扰。 [0004] Another technical effect of using the fade fluorescence intensity gradually reduce the glare, the overall decrease in fluorescence intensity, this measure reflects a part of the fluorescence characteristics of the signal and progressively deducted from the signal, eventually eliminate fluorescence interference Raman signal . 该技术采用拉曼信号在特定波数迀移区间呈现平坦这一特性来判断荧光是否被完全消减, 但其前提是仪器设计中必须包含该段不含有效信息的光谱,对仪器设计构成了限制。 The technology uses a characteristic Raman signals in this particular shift wavenumber Gan section presenting flat determines whether fluorescence is subtracted completely, but only if the instrument design must contain valid period where no spectral information, instrument design constitute constraints.

发明内容 SUMMARY

[0005] 本发明要解决的技术问题是:提供一种通过信息熵判断拉曼光谱的荧光消除程度的方法,以解决现有技术存在的增加仪器造价和复杂性、结果不真实、对仪器设计构成限制的不足之处。 [0005] The present invention is to solve the technical problem are: to provide a degree determined by the method of entropy Raman spectrum of the phosphor eliminated to solve the cost and increase the complexity of the instrument of the prior art, false result, the instrument design limit deficiencies.

[0006] 解决上述技术问题的技术方案是:一种通过信息熵判断拉曼光谱的荧光消除程度的方法,该方法是采用离散序列的信息熵作为荧光成分扣减判据,从混合信号中逐步扣减荧光,当信息熵达到最小时,混合信号中的荧光被完全消除。 [0006] achieve the above technical solution: the extent of eliminating the Raman spectrum is determined by the fluorescence information entropy method, which is a discrete sequence of information entropy deduction criterion as the fluorescent component gradually from the mixed signal deduction fluorescence, when the entropy reaches minimum, the fluorescent signal is mixed completely eliminated.

[0007] 本发明的进一步技术方案是:该方法包括以下步骤: A、 采用拉曼激光探头测量样品的混合信号,固定焦点,设定积分时间,记录2组以上不同时刻下的光谱数据S; B、 依次对后一时刻光谱数据乘以系列权值,计算与前一时刻光谱数据的差值,得到不含拉曼信号的荧光下降度量值AS; C、 对荧光下降度量值AS进行降噪,降噪后的荧光下降度量值AS作为混合信号S中含有的荧光分量Fs; D、 从混合信号中逐步扣减n*A*Fs,n为扣减的步数,η=1,2,···,Λ为扣减步长,Fs为荧光分量,并计算每步扣减n*A*Fs后的信息熵; E、 判断每步扣减n*A*Fs后的信息熵是否是最小值,如果否,则重复步骤D,如果是,则表明荧光扣减完成,得到不含荧光的纯拉曼信号。 [0007] A further aspect of the present invention are: the method comprising the steps of: A, Raman laser probe measurement sample mixed signal, fixed focus, the integration time is set, the recording spectral data S in two or more different sets of time; B, spectral data are sequentially multiplied by weights after a series of time, and calculating the difference spectrum data of the previous time, to obtain a phosphor containing no decline measure Raman signal AS; C, fluorescence decreased for noise reduction measure AS , the noise reduction decreased fluorescence aS metric fluorescent component contained in the mixed signal S Fs; D, progressively deducted from the mixed signal n * a * Fs, n is the number of deduction steps, η = 1,2, ···, Λ is the deduction step, Fs of a fluorescent component, and each step is calculated after deduction of information entropy n * a * Fs; E, determining whether each of the information entropy deduction step is n * a * Fs minimum, if not, repeat the procedure D, if yes, it indicates the completion of the deduction fluorescent, non-fluorescent to obtain pure Raman signal.

[0008]本发明的再进一步技术方案是:在步骤B中,所述的系列权值为0.95~1.05。 [0008] Still further aspect of the present invention: in step B, the series weight value of 0.95 to 1.05.

[0009]本发明的再进一步技术方案是:在步骤C中,所述的对荧光下降度量值AS进行降噪选用Savitzky-Golay滤波器,选择2阶滤波,窗口宽度为整体信号长度的1/10。 [0009] Still further aspect of the present invention: in step C, the fluorescence dropped AS metric selected for noise reduction Savitzky-Golay filter, select the second-order filter, the window width is the entire length of the signal 1 / 10.

[0010] 本发明的再进一步技术方案是:所述的步骤D包括如下具体方法: D1、按照公式 [0010] Still further aspect of the present invention is that: said step D includes the following specific methods: D1, according to the formula

Figure CN105699356AD00041

,计算混合信号的信息熵H(X),公式中P (&1)为混合信号S取第i个光强度的概率,i = 1,2,…,q,q取值为光谱所含数据点数量; D2、设定扣减步长Λ,从混合信号中逐步扣减n*A*Fs,n为扣减的步数,n=l,2,…,FS为荧光分量,并计算每步扣减n*A*Fs后的信息熵。 Calculating the mixed signal entropy H (X), the formula P (& 1) to take a mixed signal S i-th probability of the light intensity, i = 1,2, ..., q, q is the spectral values ​​contained in the data points number; D2 of, deducted set Lambda step, progressively deducted from the mixed signal n * a * Fs, n is the number of deduction steps, n = l, 2, ..., FS calculated for each step is a fluorescent component, and after the deduction of information entropy n * a * Fs.

[0011] 本发明的更进一步技术方案是:所述的扣减步长Λ为0.01~0.1。 [0011] Still further aspect of the present invention are: the deduction step Λ is 0.01 to 0.1.

[0012] 由于采用上述结构,本发明之通过信息熵判断拉曼光谱的荧光消除程度的方法与现有技术相比,具有以下有益效果: 1.可真实合理、有效地消除拉曼光谱的荧光: 本发明是采用离散序列的信息熵作为荧光成分扣减判据,从混合信号中逐步扣减荧光,当信息熵达到最小时,混合信号中的荧光被完全消除。 Compared with the prior art [0012] As a result of the above-described configuration, the present invention is determined entropy degree of fluorescence Raman spectrum elimination method has the following advantages: 1. Real reasonably effectively eliminate fluorescence Raman spectrum : the present invention is a discrete sequence of information entropy as the fluorescent component deduction criterion, progressively deducted from the mixed signal fluorescence, when the entropy reaches minimum, the fluorescent signal is mixed completely eliminated. 由于光照射激发拉曼光也会同时激发荧光,从而对拉曼光产生干扰。 Since the Raman excitation light irradiation will also excite fluorescence, Raman light to produce interference. 然而,拉曼光和荧光并不同步,拉曼所含信息量明显高于荧光;研究证实,含荧光的混合信号的不确定性总是大于纯拉曼信号,即信号完全由拉曼光谱构成,其熵值最小。 However, Raman and fluorescence are not synchronized, the amount of information contained significantly higher Raman fluorescence; study confirmed that the phosphor-containing mixed signal uncertainty is always greater than a pure Raman signal, i.e. the signal consists entirely of Raman spectroscopy The minimum entropy value. 因此,本发明可真实合理、有效地消除拉曼光谱的荧光。 Accordingly, the present invention can be reasonably true, effectively eliminating fluorescence Raman spectrum.

[0013] 2.方法简便: 由于混合信号的熵值的大小只与该信号的组成情况有关,与幅度无关,不需要标准化等其他数据预处理方法,适合于每次单一测量数据的处理;因此,本发明与需要多次测量才能采用的秩判断等方法相比,本发明的方法更为简便。 [0013] The method is simple: since the size of the entropy of the mixed signal is only related to the composition of the signal, regardless of the magnitude, does not require standardization and other data preprocessing method, each adapted to process a single measurement data; thus , the present invention is compared with the required multiple measurements in order to rank determined using other methods, the method of the present invention easier.

[0014] 3.可增加仪器设计和制造的自由度: 本发明采用信息熵判断荧光的消除程度,更为科学合理,不受仪器波数范围限制,使仪器性能得到充分发挥,增加仪器设计和制造的自由度。 [0014] 3. increase the degree of freedom in the design and manufacture of the instruments: the present invention uses entropy to eliminate the degree of fluorescence determination, more reasonable, not instrument wavenumber range limit, full performance of the instrument, instrument design and manufacture to increase of degrees of freedom. 因此,本发明解决了现有技术需要在特定波长范围判断荧光残留情况的限制,对光谱范围无特殊要求,可适应不同波长设置的仪器设计。 Accordingly, the present invention solves limitations of the prior art need to determine the residual fluorescence in a specific wavelength range of the case, no special requirements on spectral range, the instrument may be designed to accommodate different set of wavelengths.

[0015] 4.所用的设备简单、造价低: 本发明的采集要求和采集步骤与现有采集方法无差异,其设备简单、造价低,在不增加设备造价、测量附件和改变现有采集步骤的情况下,快速、准确地获得符合实际机理的不受荧光干扰的拉曼真实信号,易于推广应用。 [0015] 4. The equipment used is simple, low cost: acquisition requirements of the invention and no difference acquisition step with conventional collection method, which equipment is simple, low cost, without increasing the cost of equipment, accessories, and measuring changes in the current acquisition step under the circumstances, quickly and accurately obtain fluorescence interference from realistic real mechanism of Raman signal, easy application.

[0016] 下面,结合附图和实施例对本发明之通过信息熵判断拉曼光谱的荧光消除程度的方法的技术特征作进一步的说明。 [0016] Next, in conjunction with the accompanying drawings and the technical features of embodiments of the method determining the Raman spectrum of the phosphor elimination by the present invention, the degree of entropy further described.

附图说明 BRIEF DESCRIPTION

[0017] 图1:实施例一步骤Α中测得的光谱图, 图2:实施例一步骤B中,采用加权差减和不加权差减的光谱对比图, 图3:实施例一步骤C所述混合信号中含有的荧光分量的光谱图, 图4:实施例一步骤D中,信息熵随扣减量变化情况图, 图5:实施例一步骤E中,得到的不含荧光的拉曼信号R与原始测量的混合信号S之间的光谱对比图; 图6:在200-1800(31^1波段信号时,信息熵随扣减量变化情况图; 图7:模拟拉曼-荧光混合信号的荧光消除试验中,采用洛伦兹函数分别模拟出对应于拉曼和荧光的光谱曲线图, 图8:模拟拉曼-荧光混合信号的荧光消除试验中,1倍拉曼信号和5倍荧光信号的加和效果图, 图9:模拟拉曼-荧光混合信号的荧光消除试验中,1倍的拉曼信号加和了-1~5倍的荧光的信息熵变化情况图。 [0017] Figure 1: Example a step Α measured spectrum, Fig. 2: Example a step B, in the spectrum comparison chart weighted subtraction unweighted subtracted, and FIG. 3: Example 1 Step C fluorescence spectra of the components contained in the mixed signal, Figure 4: an embodiment of step D, entropy changes with the amount of deduction, and FIG. 5: step E in Example a, the obtained non-fluorescent pull FIG spectral comparison between the mixing signal with the original signal R S Mann measurement; FIG. 6: 200-1800 (31 ^ 1 band signal, entropy changes with the amount of deduction; Figure 7: Raman analog - fluorescence elimination of the fluorescent test mix signal using Lorentz functions are simulated Raman spectrum graph corresponds to the fluorescence and, Figure 8: Raman analog - to eliminate fluorescence assay mix signal, and a 5-fold Raman signal FIG times the additive effect of the fluorescence signal, Figure 9: Raman analog - to eliminate fluorescence assay mix signal, plus 1 times the Raman signals and -1 to 5 times the fluorescence changes of entropy FIG.

具体实施方式 detailed description

[0018] -种通过信息熵判断拉曼光谱的荧光消除程度的方法,该方法是采用离散序列的信息熵作为荧光成分扣减判据,从混合信号中逐步扣减荧光,当信息熵达到最小时,混合信号中的荧光被完全消除。 [0018] - Analyzing method kinds Raman spectrum of the phosphor elimination by the extent information entropy, which is a discrete sequence of information entropy as the fluorescent component deduction criterion, progressively deducted from the mixed signal fluorescence, when the entropy reaches the most h, the fluorescence signal is mixed completely eliminated.

[0019] 该方法包括以下步骤: A、 采用拉曼激光探头测量样品的混合信号,固定焦点,设定积分时间,记录2组以上不同时刻下的光谱数据S; B、 依次对后一时刻光谱数据乘以系列权值,该系列权值为0.95~1.05,计算与前一时刻光谱数据的差值,得到不含拉曼信号的荧光下降度量值AS; C、 选用Savi tzky-Golay滤波器对焚光下降度量值Δ S进行降噪,选择2阶滤波,窗口宽度为整体信号长度的1/10,降噪后的荧光下降度量值AS作为混合信号S中含有的荧光分量Fs; D、 从混合信号中逐步扣减n*A*Fs ,η为扣减的步数,n=l,2,…,Λ为扣减步长,Fs为荧光分量,并计算每步扣减n*A*Fs后的信息熵; D1、按照公式 [0019] The method comprises the steps of: A, Raman laser probe measurement sample mixed signal, fixed focus, the integration time is set, the recording spectral data S in two or more different sets of time; B, sequentially later time spectrum series data is multiplied by the weights, the series weight value of 0.95 to 1.05, a difference between the previous time is calculated spectral data to obtain metric decreased fluorescence free Raman signal AS; C, selected Savi tzky-Golay filter burning light decrease [Delta] S value of noise reduction, selected second order filter, the window width is 1/10 of the entire length of the signal, the noise reduction decreased fluorescence aS metric fluorescent component contained in the mixed signal S Fs; D, from deducted gradually mixed signal n * a * Fs, η is the number of deduction steps, n = l, 2, ..., Λ is the deduction step, Fs of a fluorescent component, and each step is calculated deduction n * a * after entropy Fs; D1, according to the formula

Figure CN105699356AD00051

,计算混合信号的信息熵H(X),公式中P (&1)为混合信号S取第i个光强度的概率,i = 1,2,…,q,q取值为光谱所含数据点数量; D2、设定扣减步长Λ,从混合信号中逐步扣减n*A*Fs,n为扣减的步数,n=l,2,…,FS为荧光分量,并计算每步扣减n*A*Fs后的信息熵; E、 判断每步扣减n*A*Fs后的信息熵是否是最小值,如果否,则重复步骤D,如果是,则表明荧光扣减完成,得到不含荧光的纯拉曼信号。 Calculating the mixed signal entropy H (X), the formula P (& 1) to take a mixed signal S i-th probability of the light intensity, i = 1,2, ..., q, q is the spectral values ​​contained in the data points number; D2 of, deducted set Lambda step, progressively deducted from the mixed signal n * a * Fs, n is the number of deduction steps, n = l, 2, ..., FS calculated for each step is a fluorescent component, and after the deduction of the entropy n * a * Fs; E, each step is determined whether the deduction entropy n * a * Fs is the minimum, if not, repeat the procedure D, if yes, it indicates the completion of the fluorescence deduction to give a pure non-fluorescent Raman signal.

[0020] 以下是本发明的具体实施例: 实施例一: 一种通过信息熵判断蔗糖拉曼光谱的荧光消除程度的方法,该方法包括以下步骤: A、采用拉曼激光探头785nm激光激发,测量蔗糖拉曼光谱,固定焦点,设定积分时间l〇s,时间间隔30s测量2次,记录所得混合信号Su S2,如图1中所示,Si为时刻1的测量光谱,S2 为时刻2的测量光谱; B、 调节时刻2光谱的权值为1.028,与前一时刻光谱差减,得到有效消除其中的拉曼成分的荧光下降降度量值AS,分别将加权后差减的光谱S3与不加权直接差减的光谱S4作对比如图2所示,从图2中可看出,采用加权差减,可以有效消除其中的拉曼成分; C、 选用Savi tzky-Golay滤波器对焚光下降度量值Δ S进行降噪,选择2阶滤波,窗口宽度为91;降噪后的荧光下降度量值AS作为混合信号S中含有的荧光分量Fs,如图3所示; D、 从混合信号中逐步扣 [0020] The following are specific embodiments of the invention: Example I: one kind of entropy is determined by a Raman spectrum of the phosphor Sucrose elimination level, the method comprising the steps of: A, using 785nm laser excitation Raman laser probe, Raman spectra measure sucrose, fixed focus, to set the integration time l〇s, 30s intervals measured twice, recording the resulting mixed signal Su S2, as shown in FIG. 1, Si is a measured spectrum of time, S2 is a time 2 the measured spectrum; right B, spectrum 2 is adjusted time 1.028, at a previous time spectral subtraction, effectively eliminate fluorescence dropped down metric AS wherein a Raman component, respectively weighted and subtracted spectrum S3 unweighted spectral subtraction directly against such S4 shown in FIG. 2, can be seen in FIG. 2, weighted subtraction, can effectively eliminate Raman ingredient therein; C, Savi tzky-Golay filter selection decline burning light metric [Delta] S for noise reduction, selected second order filter, the window width is 91; noise fluorescence decrease after aS metric fluorescent component contained in the mixed signal Fs of S, 3; D, from the mixed signal gradually buckle 减n*A*Fs,n为扣减的步数,n=l,2,···,Λ为扣减步长,Fs为荧光分量,并计算每步扣减n*A*Fs后的信息熵,其具体方法是: D1、按照公式 Save n * A * Fs, n is the number of deduction steps, n = l, 2, ···, Λ is the deduction step, Fs of a fluorescent component, and each step is calculated deduction n * A * Fs after information entropy, specific method is: D1, according to the formula

Figure CN105699356AD00061

,计算混合信号的信息熵,公式中P(ai)S 混合信号S取第i个光强度的概率,i = 1,2,…,q,q取值为光谱所含数据点数量; D2、设定扣减步长Λ,从混合信号中逐步扣减n*A*Fs,n为扣减的步数,n=l,2,…,FS为荧光分量,并计算每步扣减n*A*Fs后的信息熵; E、 判断每步扣减n*A*Fs后的信息熵是否是最小值,如果否,则重复步骤D,如果是,则表明荧光扣减完成,得到不含荧光的纯拉曼信号。 Calculating the mixed signal information entropy, the formula P (ai) S take the first mixed signal S i probability of the light intensity, i = 1,2, ..., q, q is the number of spectral values ​​contained in the data points; D2 of, Lambda set deduction step, progressively deducted from the mixed signal n * a * Fs, n is the number of deduction steps, n = l, 2, ..., FS is a fluorescent component, and each step is calculated deduction n * a * information entropy of Fs; E, determining whether the information entropy deduction each step n * a * Fs is the minimum, if not, repeat the procedure D, if yes, it indicates the completion of the deduction fluorescence, containing no fluorescence pure Raman signal. 图4是信息熵随扣减量变化情况,在FS的5.83倍时,信息熵出现最小值,即是从原始的混合信号S中扣除对应的5.83倍FS后,得到不含荧光的拉曼信号R;图5为得到的不含荧光的拉曼信号R与原始测量的混合信号S之间的光谱对比图。 FIG 4 is entropy changes with the amount of deduction, when 5.83 times of FS, minimum entropy occurs, that is, after deduction of 5.83 times the corresponding mixed signal FS from the original S, the Raman signal obtained non-fluorescent R; FIG spectral comparison between FIG. 5 is a non-fluorescent Raman signal obtained mixed signal S R and the original measurement.

[0021] 本申请的发明人还选择了200-1800(^1波段信号计算信息熵,如图6所示,在荧光分量FS的5.88倍出现最小值,与采用实施例一中在200-3000(31^ 1波段信号的计算的信息熵最小值时的5.8 3*FS的误差小于1 %,表明本发明可以不依赖特定的信号范围,而获得一致的有效结果。 [0021] The inventors of the present application also selected 200-1800 (^ 1 band signal calculation information entropy, as shown, a minimum value appears at 5.88 FS fluorescent component 6, an embodiment employing in Example 200-3000 5.8 3:00 of entropy computed minimum value (1 ^ 31 * band error signal FS is less than 1%, indicating that the present invention may not rely on a specific signal range, and achieve effective results consistent.

[0022] 采用信息熵判断荧光的消除程度,更为科学合理,不受仪器波数范围限制,使仪器性能得到充分发挥,增加仪器设计和制造的自由度。 [0022] The degree of fluorescence is determined entropy eliminated more reasonable, not instrument wavenumber range limit, full performance of the instrument, the degree of freedom in the design and manufacture of the instrument. 本发明解决了现有技术中需要在特定波长范围判断荧光残留情况的限制,对光谱范围无特殊要求,可适应不同波长设置的仪器设计。 The present invention addresses the limitations of the prior art need to determine the residual fluorescence in a specific wavelength range of the case, no special requirements on spectral range, the instrument may be designed to accommodate different set of wavelengths. 不增加设备复杂程度和改变现有测量习惯的情况下,能够快速、准确地获得符合实际机理的不受荧光干扰的拉曼真实信号。 Without increasing the complexity of the measurement equipment and change existing habits, can quickly and accurately obtain fluorescence interference from realistic real mechanism of Raman signal.

[0023] 此外,为了应证信息熵具有最小值时荧光含量为0,本申请的发明人还作了模拟拉曼-荧光混合信号中的荧光消除试验: 1.采用洛伦兹函数分别模拟出对应于拉曼和荧光的光谱曲线,如图7所示。 [0023] Further, in order entropy should permit a phosphor content of the minimum value is 0, the inventors of the present application also been simulated Raman - fluorescence mixed signal elimination test: 1. The use of Lorentzian functions are simulated Raman spectral curve corresponds to the fluorescence and, as shown in FIG.

[0024] 2.将模拟的拉曼和荧光信号加和,可得到模拟的混合信号。 [0024] 2. The simulated Raman and fluorescence signals summed and mixed to obtain an analog signal. 图8为1倍拉曼信号和5 倍荧光信号的加和效果。 8 is an additive effect of the Raman signal and 5x times fluorescent signal.

[0025] 3.计算模拟拉曼信号分别加和不同含量的荧光后的信息熵值。 [0025] 3. Raman signals are analog computing entropy values ​​plus the different levels of fluorescence. 图9为1倍的拉曼信号加和了-1~5倍的荧光的信息熵变化情况,可以看出,信息熵具有最小值时荧光含量为0, 输出的即为不含荧光的拉曼信号。 9 is a Raman signal is applied twice and the entropy-1 to 5-fold change in fluorescence case, it can be seen, when the content of fluorescent entropy minimum value is 0, that is, non-fluorescent output Raman signal.

Claims (6)

  1. 1. 一种通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:该方法是采用离散序列的信息赌作为巧光成分扣减判据,从混合信号中逐步扣减巧光,当信息赌达到最小时,混合信号中的巧光被完全消除。 CLAIMS 1. A method of determining the Raman spectrum of light to eliminate the degree of coincidence by the bet information, wherein: the method is to use the information as a sequence of discrete gambling coincidence criterion deducted light component, from the mixed signal light gradually deducted Qiao , when the information reaches the minimum bet, Qiao mixed signal light is completely eliminated.
  2. 2. 根据权利要求1所述的通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:该方法包括W下步骤: A、 采用拉曼激光探头测量样品的混合信号,固定焦点,设定积分时间,记录2组W上不同时刻下的光谱数据S; B、 依次对后一时刻光谱数据乘W系列权值,计算与前一时刻光谱数据的差值,得到不含拉曼信号的巧光下降度量值AS; C、 对巧光下降度量值AS进行降噪,降噪后的巧光下降度量值AS作为混合信号S中含有的巧光分量Fs; D、 从混合信号中逐步扣减η*Δ冲S,η为扣减的步数,n=l,2,…,Δ为扣减步长,Fs为巧光分量,并计算每步扣减η*Δ冲S后的信息赌; Ε、判断每步扣减η*Δ冲S后的信息赌是否是最小值,如果否,则重复步骤D,如果是,则表明巧光扣减完成,得到不含巧光的纯拉曼信号。 The bet information by the method of claim 1 determining the degree of coincidence to eliminate light Raman spectrum, characterized in that: the method comprises the steps of W: A, mixed-signal Raman laser probe measurement sample, a fixed focus , the integration time is set, the recording spectral data S in the two groups at different times W; B, spectral data are sequentially multiplied by weights W series after a time, a time difference between the previous calculation of the spectral data, obtained free Raman Qiao the aS signal light is decreased metric; C, to decrease light clever aS metric for noise reduction, the noise reduction decreased metric aS clever light as clever light components contained in the mixed signal S Fs; D, from the mixed signal after deduction gradually washed η * Δ S, [eta] is the number of deduction steps, n = l, 2, ..., Δ is the deduction step, as clever Fs of light components, each step is calculated and deducted punch η * Δ S bet information; Epsilon, each step is determined deduction η * Δ S red bet information after whether the minimum, if not, repeat the procedure D, if yes, it indicates the completion of the deduction clever light, light containing no clever pure Raman signal.
  3. 3. 根据权利要求2所述的通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:在步骤Β中,所述的系列权值为0.95~1.05。 3. bet information by the determination method according to claim 2 coincidence degree light eliminate Raman spectrum, wherein: in step Β, the series weight value of 0.95 to 1.05.
  4. 4. 根据权利要求2所述的通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:在步骤C中,所述的对巧光下降度量值AS进行降噪选用Savitzky-Golay滤波器,选择2 阶滤波,窗口宽度为整体信号长度的1/10。 The information recited by claim 2 bet coincidence determination method to eliminate the degree of light Raman spectrum, wherein: in step C, the decrease of light Qiao the AS noise metric selection Savitzky-Golay filter, select the second-order filter, the window width is 1/10 of the entire length of the signal.
  5. 5. 根据权利要求2所述的通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:所述的步骤D包括如下具体方法: D1、按照公式 The bet information by the determination method according to claim 2 clever enough to dissolve the Raman spectrum of light, characterized in that: said step D includes the following specific methods: Dl, according to the formula
    Figure CN105699356AC00021
    计算混合信号的信息赌H(X),公式中P (ai)为混合信号S取第i个光强度的概率,i = 1,2,…,q,q取值为光谱所含数据点数量; D2、设定扣减步长Δ,从混合信号中逐步扣减η*Δ冲s,n为扣减的步数,n=l,2,···,Fs为巧光分量,并计算每步扣减η*Δ冲S后的信息赌。 Calculating the mixed signal information bet H (X), the formula P (ai) is the mixed signal S takes the i-th probability of the light intensity, i = 1,2, ..., q, q is the number of spectral values ​​contained in the data points ; D2 of, deducted set step size [Delta], from the mixed signal progressively deducted punch η * Δ s, n is the number of deduction steps, n = l, 2, ···, Fs is a clever light component, and calculates each step deduction η * Δ bet information after red S.
  6. 6. 根据权利要求5所述的通过信息赌判断拉曼光谱的巧光消除程度的方法,其特征在于:所述的扣减步长Δ为0.01~0.1。 Through the information according to claim 5 bet coincidence determination method to eliminate the degree of light Raman spectrum, wherein: said deduction step size Δ of 0.01 to 0.1.
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