METHOD AND SPECTROSCOPIC ANALYSIS APPLIANCE, ESPECIALLY FOR ANALYSING FOOD, WITH MULTI-CHANNEL TREATMENT OF SPECTRAL DATA

• US 20120280146A1
• Filed: 12/08/2010
• Published: 11/08/2012
• Est. Priority Date: 12/16/2009
• Status: Active Grant

• Current Assignee: Spectralys Innovation, Co.
• Original Assignee: Spectralys Innovation, Co.
• Inventors: Rizkallah, Jad, Birlouez-Aragon, Inès
• Granted Patent: US 8,987,686 B2
• Time in Patent Office: Days
• US Class Current: 250/459.1
• CPC Class Codes: G01N 2021/6419 Excitation at two or more wavelengths
• CPC Class Codes: G01N 21/64 Fluorescence; Phosphorescence
• CPC Class Codes: G01N 2201/129 Using chemometrical methods
• CPC Class Codes: G01N 33/02 Food

Abstract

The invention relates to a method for the spectroscopic analysis of at least one sample, using a method for analysing spectroscopic data based on a multi-channel statistical model, said method comprising: the illumination of said or each sample to be analysed by a plurality of luminous excitation rays with respective wavelengths; the acquisition and the pre-treatment of frontal fluorescence spectra, each spectrum corresponding to a respective luminous excitation ray; for each sample, the calculation of a score vector by applying said multi-channel statistical model to the pre-treated spectra; and the determination of at least one parameter selected from a quality indicator of said or each sample and a parameter characterising a method that has been applied to said or each sample, from said score vector; the method being characterised in that the average spectral distance between the luminous excitation rays is at least 50 nm, over a spectral range of at least 100 nm. The invention also relates to an appliance for implementing such a method.

Claims

1. Method for spectroscopic analysis of at least one sample implementing a method for analysis of spectroscopic data based on a multi-way statistical model, which method includes:

a) the illumination of said or of each sample to be analyzed by a plurality of excitation light radiations with respective wavelengths;

b) the acquisition of front-face fluorescence spectra of said or of each sample, each corresponding to a respective excitation light radiation;

c) a pre-processing of the fluorescence spectra acquired;

d) for each sample, the calculation of a score vector by application to the pre-processed spectra of said multi-way statistical model, identified by a fluorescence excitation loading vector and by an emission loading vector; and

e) the determination of at least one parameter chosen from a quality indicator of said or of each sample and a parameter characterizing a method to which said or each sample has been subjected, on the basis of said score vector;

the method being characterized in that the average spectral gap between said excitation light radiation is at least 50 nm over a spectral range of at least 100 nm.

2. Method according to claim 1, in which the number of excitation light radiations and corresponding fluorescence spectra for each sample is between two and six over a spectral range of at least 100 nm.

3. Method according to claim 1, also including a preliminary calibration phase comprising:

i) the illumination of a plurality of calibration samples by said excitation light radiation;

ii) the acquisition of front-face fluorescence spectra of the samples, corresponding to said excitation light radiation;

iii) a pre-processing of the acquired fluorescence spectra;

iv) the determination, by an iterative method, of said loading excitation and emission vectors of the multi-way model, as well as a score vector for each calibration sample; and

v) the determination of a regression function linking said scores to the known values of said or of each parameter for said calibration samples.

4. Method according to claim 1, in which the fluorescence spectra are pre-processed by subtracting a contribution due to the first-order Rayleigh scattering of the excitation light radiation, with said contribution being calculated by means of a generalized linear model.

5. Method according to claim 4, in which said generalized linear model is determined on the basis of a first portion (RD) of the spectrum to be pre-processed, including only said contribution due to the Rayleigh scattering, and is used to predict the Rayleigh scattering contribution in a second portion (RP) of said spectrum in which it is superimposed with a fluorescence contribution.

6. Method according to claim 1, in which the fluorescence spectra are pre-processed by being normalized.

7. Method according to claim 1, in which the fluorescence spectra of a plurality of samples, for calibration and/or to be analyzed, are pre-processed by performing a multiplicative scatter correction.

8. Method according to claim 1, in which said multi-way statistical model is a PARAFAC model, with the fluorescence spectra of each sample being represented in concatenated form.

9. Method according to claim 8, in which the loading vectors of said PARAFAC model are determined by an iterative method that is stopped when the reduction of the loss function due to the last iteration goes below a threshold value between 10⁻

4 and 10<sup>−

2</sup>.

10. Method according to claim 1, in which said multi-way statistical model is an NPLS model, with the fluorescence spectra of each sample being represented in concatenated form.

11. Method according to claim 10, in which the fluorescence spectra are pre-processed by orthogonal signal correction.

12. Method according to claim 1, in which said excitation light radiation includes:

a first radiation with a wavelength of between 270 and 300 nm;

a second radiation with a wavelength of between 300 and 360 nm; and

a third radiation with a wavelength of between 400 and 500 nm.

13. Method according to claim 1, in which said or at least one said parameter to be determined is chosen from:

the content of a substance of interest in said or in each sample;

a microbial load of said or of each sample; and

a sterilizing, pasteurizing or cooking value, or a time-temperature product, of a method to which said or each sample has been subjected.

14. Method according to claim 1, in which the samples to be analyzed and for calibration are samples of a product chosen from:

a food and a drug.

15. Use of a method according to claim 14 to measure the change in nutritional, microbiological and/or toxicological properties of a food during its preparation or preservation.

16. Appliance for spectroscopic analysis of at least one sample comprising:

a set of light sources for illuminating said or each sample to be analyzed by respective excitation light radiations, having different wavelengths with an average spectral gap of at least 50 nm over a spectral range of at least 100 nm;

means for acquisition (M, D) of the front-face fluorescence spectra emitted by said or each sample when illuminated by said excitation light radiation; and

means for processing the fluorescence spectra acquired, suitable for implementing a method according to claim 1.

17. Appliance for spectroscopic analysis according to claim 16, comprising between two and six of said light sources.

18. Appliance according to claim 17, comprising:

a first light source emitting radiation at a wavelength of between 270 and 300 nm;

a second light source emitting radiation at a wavelength of between 300 and 360 nm; and

a third light source emitting radiation at a wavelength of between 400 and 500 nm.