Device for the spectroscopic analysis of a sample and method for analyzing a sample by means of such a device

Abstract

The invention relates to a device (1) for analyzing a heterogeneous sample (S), the device (1) comprising a measurement module (100) having a reservoir (110) configured to contain the sample (S), a first infrared spectroscopy subassembly (120) and a second fluorescence spectroscopy subassembly (130). The first subassembly comprises a diffusing optical element (140) positioned to allow reliable infrared spectroscopy measurements with high precision without degrading fluorescence spectroscopy measurements occurring on the same sample. The device further comprises a processing module (200) connected to the measurement module (100) by a communication network (300) and comprising a processor (220) configured to analyze data obtained by infrared spectroscopy and fluorescence spectroscopy.

Description

Technical Field

[0001] This invention relates to the field of spectroscopic analysis, and more particularly to infrared spectroscopy and fluorescence spectroscopy. The coupling of these two techniques makes it possible to provide complementary or even synergistic information on the same sample.

[0002] This invention relates to an apparatus for analyzing samples. The invention further relates to a method for analyzing samples using such an apparatus.

[0003] Within the scope of this invention, the sample is more specifically a heterogeneous sample, which can be a solid (grains, crushed biscuits or crackers, raw dough) or a powder (flour, milk powder). In the sense of this invention, a heterogeneous sample is a sample containing elements of different and highly absorbent sizes. For example, the sample may contain impurities. That is, in the case of a particulate sample, the heterogeneity of the sample can also preserve its particle size.

[0004] This invention has applications in the agricultural industry, and particularly in the cereal or dairy industries. Specifically, it aims to allow those skilled in the art to analyze samples at different stages of sample development. In the agricultural industry, especially in cereals or dairy, industrial processes require precise understanding of the characteristics and quality indicators of the samples being analyzed (Hagberg drop number for wheat, alveograph, farinograph, or even bread-making tests for raw dough). As part of this, analysis of samples using spectroscopic techniques makes it possible to extract all the physicochemical information readily conveyed in these different functionalities within tens of seconds by establishing a calibration between the spectral information and the criteria describing the product's functionality. Background Technology

[0005] Spectroscopic instruments employing various analytical methods are known, making it possible to obtain physicochemical information about samples. The analytical methods used in this regard are conventional fluorescence spectroscopy and infrared spectroscopy.

[0006] Document WO 2019 / 118800 A1 discloses a commercially available measuring instrument that enables physicochemical analysis of samples using both infrared and fluorescence spectroscopy measurements. The instrument comprises a single source and a monochromator that allows modification of the wavelength of an emitted light beam within a spectral range suitable for both types of measurements. The instrument includes a set of mirrors and reflectors, which allows the light beam emitted from the source to take different optical paths, at least one of which is dedicated to infrared spectroscopy measurements and at least another to fluorescence spectroscopy measurements.

[0007] If the instrument actually makes it possible to measure the same sample, then the sample volume that can be analyzed is 1 cm³. 3 In practice, this type of instrument is primarily used in academic settings where the observed samples are often homogeneous model samples with very small dimensions. However, if the volume represents many particles, it is less suitable for analyzing highly absorbent samples. In contrast, in agricultural industries (especially cereals or dairy products), the samples studied (grains, dough, powders, etc.) are often highly heterogeneous not only in size, shape, and even composition, but also in terms of volume, representing the contents of silos (thousands of cubic meters). Furthermore, if the instrument makes it possible to analyze samples that are not highly absorbent, such as liquid samples, thin layers, paper layers, gemstones, etc., it is unsuitable for analyzing highly absorbent samples.

[0008] To accurately measure parameters of heterogeneous samples as defined above and to meet industry standards, suitable equipment has been developed.

[0009] From document EP 1850117 A1, spectroscopic analysis apparatus is known that allows for the measurement of such samples from two types of measurements. The apparatus includes a first module specifically designed for infrared spectroscopic analysis. This module includes a chamber equipped with a source emitting near-infrared and infrared electromagnetic radiation to illuminate the sample, a network monochromator-type detector or filter for reading the transmission spectrum of the sample, and a placement intended to contain the sample. The apparatus also includes a second module specifically designed for fluorescence spectroscopic analysis. This module includes a chamber containing a source emitting electromagnetic radiation intended to illuminate the sample, causing the sample to emit a typical fluorescence signal under the influence of this radiation. The module also includes a fluorescence detector capable of measuring the signal emitted by the sample and a placement for reserving the sample.

[0010] Therefore, two operating modes, each associated with a specific configuration, are possible. In the first configuration, the material sample is pre-divided into two samples, each moving toward a specific module for the purpose of performing a particular type of measurement, while in the second configuration, the material sample moves sequentially from one module to another.

[0011] When a sample is split into two, additional steps are required to separate them. Furthermore, the volume of a sample analyzed by infrared spectroscopy will never be the same as the volume of a sample analyzed by fluorescence spectroscopy, because the two samples are always different; they both originate from the same starting sample, due to the heterogeneity of that starting sample.

[0012] When the sample is moved sequentially between the two modules of the instrument, additional operations are required to move the sample from one module to the other. Furthermore, with this configuration, due to dispersion, it is impossible to guarantee that the volume of the sample analyzed by infrared spectroscopy covers the same physicochemical reality as the same volume of the independently tested sample analyzed by fluorescence spectroscopy. In fact, if the solid sample is heterogeneous, it is always suspected that the analyzed subsample does not represent the initial sample, and even if the sample does represent the initial sample, its position within the measurement chamber will differ during its movement between the two modules. This will inevitably affect the measurement.

[0013] Therefore, the aforementioned spectroscopic analysis equipment has several drawbacks, as it makes it impossible to analyze heterogeneous samples with different and highly absorbent sizes, or it makes it impossible to perform infrared and fluorescence spectroscopic measurements on the same sample without having to move the sample or split it into two.

[0014] As a result, existing equipment makes it impossible to optimally couple data obtained through infrared spectroscopy and fluorescence spectroscopy, because an image of a sample measured by infrared spectroscopy does not correspond to an image of the same sample measured by fluorescence spectroscopy. Summary of the Invention

[0015] This invention makes it possible to overcome the above-mentioned disadvantages and provides a device for analyzing heterogeneous samples, characterized in that it comprises:

[0016] - Measurement module, including:

[0017] A storage container, configured to hold the sample and equipped with a first wall and a second wall opposite to the first wall,

[0018] A first infrared spectroscopy sub-component includes: a first excitation source configured to emit electromagnetic radiation in an infrared field and / or a near-infrared field toward a first wall of a storage device, the first wall being transparent to infrared electromagnetic radiation; and a first means for acquiring a transmission spectrum.

[0019] A second fluorescence spectroscopy sub-assembly includes: at least one second excitation source configured to emit electromagnetic radiation in an ultraviolet and / or visible field toward a second wall of a storage device, the second wall being transparent to the electromagnetic radiation such that the volume of the sample illuminating the first excitation source at least partially corresponds to the volume of the sample illuminating the second excitation source; and a second means for acquiring the fluorescence spectrum of the sample. The first sub-assembly includes a diffusing and transparent optical element for the electromagnetic radiation emitted by the first excitation source, the optical element being positioned between the first excitation source and the first wall of the storage device or between the second wall of the storage device and the first acquisition means, outside the optical path of the electromagnetic radiation emitted by the second excitation source, and collecting the fluorescence signal emitted by the sample outside the solid angle of the fluorescence signal when exposed to the electromagnetic radiation emitted by the second excitation source.

[0020] - A processing module, which is connected to the measurement module via a communication network and includes a processor configured to analyze data obtained by infrared spectroscopy and fluorescence spectroscopy.

[0021] Therefore, an apparatus is provided that makes it possible to analyze heterogeneous solid or powdery samples of varying sizes and high absorbency, such as grains, flour, and dough. Furthermore, this apparatus makes it possible to perform infrared and fluorescence spectroscopy measurements in a single module, without having to move the sample to be analyzed from one module to another or split it into two parts for each type of measurement. In this configuration, the volume of the sample obtained through infrared spectroscopy always corresponds at least partially to the volume of the sample obtained through fluorescence spectroscopy, making it possible to correlate data from both types of measurements. Additionally, the reduced number of operations makes it possible to minimize the effects of these measurements over time and the time spent performing them. This makes the apparatus according to the invention particularly suitable for physicochemical analysis in industrial environments.

[0022] Problems related to measuring the transmittance of highly absorptive samples have been addressed using diffuse and transparent optical elements. Conventionally, when seeking infrared spectroscopic measurements (transmittance and / or reflectance) of heterogeneous samples of varying sizes and highly absorptive properties, a difference in transmitted light intensity exists between measurements without and with the sample, resulting in an intensity ratio of approximately 20,000. To correct this problem, two natural solutions exist. The first involves adding an absorptive element to the optical path between the source and the detection device during measurements without the sample. This absorptive element makes it possible to obtain comparable intensities with and without the sample, but alters the optical path between the two measurements. Therefore, the added "component" must be accounted for and potentially removed from the obtained spectrum, which can prove complex. The second solution involves altering (i.e., attenuating) the spectrum of the source itself by varying the light intensity between the two measurements. The resulting problem is the repeatability of the measurements.

[0023] Diffusion and transparent optical elements make it possible to diffuse the radiation emitted by the source during infrared spectroscopy measurements without a sample, and thus make it possible to reduce the intensity of light transmitted to the detector during this measurement. However, during measurements with a sample, the radiation emitted by the source diffuses due to the sample, but in measurements smaller than the heterogeneous sample itself, it constitutes a neutral and passive element due to the varying size and highly absorptive nature of the element, as it attenuates the source radiation almost nothing compared to the attenuation caused by the sample itself, resulting in no information loss. Therefore, the intensity ratio between two measurements can be significantly reduced without extending the measurement time, increasing the optical path length, adding any elements to the excitation source, and / or changing the spectrum of the excitation source. Thus, compared to certain solutions of the prior art, the present invention makes it possible to improve the repeatability of these measurements, provide greater robustness, and make it possible to avoid the need to modify the source between two measurements.

[0024] However, the integration of such diffused optical elements within a single measurement chamber of the device (even fluorescence measurements must be performed on the same sample, which is inherently very sensitive to diffusion) is far from sufficient. In response to this problem, the diffused optical element is positioned between the first excitation source and the first wall of the reservoir, or between the second wall of the reservoir and the first acquisition device, outside the optical path of the electromagnetic radiation emitted by the second excitation source and outside the solid angle used to collect the fluorescence signal emitted by the sample when exposed to the electromagnetic radiation emitted by the second excitation source. By positioning it in this way, infrared spectroscopy measurements can be performed on heterogeneous samples of different sizes and with very high absorbency without interfering with fluorescence spectroscopy measurements. Therefore, such a protected device makes it possible to perform reliable infrared and fluorescence spectroscopy measurements on the same sample with high accuracy.

[0025] The device of the present invention makes it possible to improve the consistency between the image of a sample measured by infrared spectroscopy and the image of a sample measured by fluorescence spectroscopy, and thus makes it possible to optimize the coupling of data obtained by infrared spectroscopy and fluorescence spectroscopy.

[0026] Different features of the present invention that can be considered together or separately:

[0027] - Optical elements form the first wall of the storage device.

[0028] - The optical element is located between the first excitation source and the first wall of the storage, and on the optical path between the first excitation source and the first acquisition device.

[0029] - The first wall of the storage container can move along an axis perpendicular to the plane that passes through the first wall.

[0030] - The second wall of the storage device is anti-reflective against electromagnetic radiation emitted by the second source.

[0031] - The second excitation source is located between the second wall and the first acquisition device.

[0032] - The axis passing through the second acquisition device and the intermediate plane and substantially perpendicular to the second wall of the storage device forms an angle α with respect to the axis passing through the first excitation source and the second acquisition device.

[0033] - The first excitation source includes a high-power halogen incandescent source.

[0034] -(various) second excitation sources emit monochromatic electromagnetic radiation,

[0035] -(the second source includes one (or more) LEDs,

[0036] The device includes a housing for receiving and holding a sample system, the housing including an inner surface on which the holding system rests.

[0037] - The device includes a sample preservation system, comprising:

[0038] - A storage device comprising a first glazed component equipped with a first wall and a second glazed component equipped with a second wall, the first glazed component being detachably mounted on the second glazed component.

[0039] - A support block for positioning and retaining the system, the support block including a connecting part and a base, the base being bent in the device with the connecting part.

[0040] - A detachable portion, including a housing for receiving a storage device, wherein the second enamel component is fixed to the detachable portion, the detachable portion being detachably connected relative to the connecting portion.

[0041] - An articulated portion including an opening, the articulated portion pivoting on a support portion and capable of passing through an installation position, wherein the articulated portion is away from the removable portion in a use position, wherein the articulated portion is folded downward on the removable portion, the opening being opposite to the storage unit, the articulated portion including a compressible device that, when the articulated portion is in the use position, makes it possible to abut the holding system against the inner surface of the housing of the module receiving the holding system.

[0042] The present invention also relates to a method for analyzing samples using the device described above, the method comprising the following steps:

[0043] A) Acquire the transmission spectrum of the sample using the first infrared spectroscopy sub-component.

[0044] B) Acquire the fluorescence spectrum of the sample using a second fluorescence spectroscopy unit.

[0045] C) By means of a processing module, data obtained through infrared spectroscopy and fluorescence spectroscopy are analyzed, and the processor is configured to determine at least one criterion characterizing the sample from the data from the analysis.

[0046] D) By means of a processing module, data obtained through infrared spectroscopy and fluorescence spectroscopy are coupled at the spectral level through the concatenation of pre-processed spectra and the correlation of fractions from each spectral decomposition to construct linear regression or nonlinear models and obtain calibration of descriptive criteria for sample status, such as technical, perceptual, or nutritional and hygiene quality criteria.

[0047] Brief description of the attached figures

[0048] Other objects and features of the invention will become clearer in the following description taken with reference to the accompanying drawings, in which:

[0049] [ Figure 1a ] Figure 1a This is a schematic representation of an analytical apparatus according to a first embodiment of the present invention, wherein an optical element is positioned between a first excitation source and a first wall of a storage device, the optical element forming part of the storage device.

[0050] [ Figure 1b ] Figure 1b This is a schematic representation of an analytical apparatus according to an embodiment of the present invention, wherein an optical element is positioned between a first excitation source and a first wall of a memory, the optical element being a different element of the memory.

[0051] [ Figure 1c ] Figure 1c This is a schematic representation of an analysis apparatus according to an embodiment of the present invention, wherein optical elements are located between the second wall of the storage device and the first excitation source.

[0052] [ Figure 2a ] Figure 2a yes Figure 1a Side view of the analytical equipment.

[0053] [ Figure 2b ] Figure 2b yes Figure 1b Side view of the analytical equipment.

[0054] [ Figure 3 ] Figure 3 This is a perspective view of the support structure used for the second excitation source.

[0055] [ Figure 4a ] Figure 4a A perspective view of a system for holding powdery, viscous, or doughy samples, according to the invention, for use in an apparatus for analyzing samples.

[0056] [ Figure 4b ] Figure 4b This is a perspective view of the retaining system in Figure 4, showing one of the faces of the retaining system.

[0057] [ Figure 5 ] Figure 5 Commentary Figure 4a and Figure 4b The diagram below shows the closed and exploded view of the memory of the retention system.

[0058] [ Figure 6a ] Figure 6a The text describes the fluorescence-related components of the original spectrum obtained during step B) by applying the method according to the invention (solid line) to a barley sample and by using a reference method (dashed line) known from the prior art for an excitation wavelength of 340 nm.

[0059] [ Figure 6b ] Figure 6b Corresponding to after Gaussian filtering Figure 6a The spectrum,

[0060] [ Figure 6c ] Figure 6c The explanation describes a series of spectra obtained on the same barley sample during step B) at an excitation wavelength of 340 nm by repeating the method according to the invention.

[0061] [ Figure 6d ] Figure 6d The explanation describes a series of spectra obtained from the same barley sample using fluorescence spectroscopy with an excitation wavelength of 340 nm, obtained from reference methods known in the prior art.

[0062] [ Figure 6e ] Figure 6e The commentary came from Figure 6c The residue of each spectrum relative to the average spectrum,

[0063] [ Figure 6f ] Figure 6f The commentary came from Figure 6d The residue of each spectrum relative to the average spectrum,

[0064] [ Figure 7a ] Figure 7a The explanation describes the fluorescence-related components of the original spectrum obtained during step B) by applying the method according to the invention (solid line) to a barley sample and by using a reference method (dashed line) known from the prior art for an excitation wavelength of 385 nm.

[0065] [ Figure 7b ] Figure 7b Corresponding to after Gaussian filtering Figure 7a The spectrum,

[0066] [ Figure 7c ] Figure 7c The explanation describes a series of spectra obtained on the same barley sample during step B) at an excitation wavelength of 385 nm by repeating the method according to the invention.

[0067] [ Figure 7d ] Figure 7d The explanation describes a series of spectra obtained from the same barley sample using fluorescence spectroscopy with an excitation wavelength of 385 nm, obtained from reference methods known in the prior art.

[0068] [ Figure 7e ] Figure 7e The commentary came from Figure 7c The residue of each spectrum relative to the average spectrum,

[0069] [ Figure 7f ] Figure 7f The commentary came from Figure 7d The residue of each spectrum relative to the average spectrum,

[0070] [ Figure 8a ] Figure 8a The explanation describes the PLS regression (RMSECV = 0.022%) obtained by linking the values ​​measured by infrared spectroscopy using reference methods known in the prior art (x-axis) and the predicted values ​​obtained through cross-validation for each sample of 204 batches of flour.

[0071] [ Figure 8b ] Figure 8b The explanation describes the MLR regression (RMSECV = 0.018%) obtained by linking the values ​​measured by fluorescence spectroscopy using reference methods known from the prior art (x-axis) and the predicted values ​​obtained through cross-validation for each sample of 204 batches of flour.

[0072] [ Figure 9 ] Figure 9 The explanation describes a continuous PLS regression (RMSECV = 0.008%) achieved by combining the values ​​of wheat flour ash measured by infrared spectroscopy and fluorescence spectroscopy (horizontal axis) with the predicted values ​​obtained by cross-validation (vertical axis) for each sample of 204 batches of flour in order to construct a calibration.

[0073] The detailed description of the present invention refers to Figure 1a The present invention relates to a device 1 for analyzing a sample S, the device comprising a measurement module 100 and a processing module 200 connected to the measurement module 100.

[0074] The measurement module 100 includes a storage 110 for accommodating a sample S, a first infrared spectroscopy sub-component 120, and a second fluorescence spectroscopy sub-component 130.

[0075] Although the first infrared spectroscopy sub-component 120 and the second fluorescence spectroscopy sub-component 130 differ in the elements that constitute them, their elements are located in a common module. Therefore, unlike known systems, the first sub-component 120 and the second sub-component 130 do not form sub-modules that are spatially defined from each other, such as two simply juxtaposed boxes, but rather their elements are optimally arranged within a single measurement module 100.

[0076] As will be seen in detail below, this optimal arrangement makes it possible to perform infrared and fluorescence spectroscopy measurements separately by means of the first sub-component 120 and the second sub-component 130 without moving or separating the sample. This makes it possible to reduce the number of operations, analyze strictly identical samples, and also improve the reproducibility of these measurements. Furthermore, the time frame for performing two measurements on the same sample is established to be only a little more than one minute, which allows the manufacturer to derive quantitative criteria for particles from it in a short time, which can be satisfactory in terms of real-time performance. As will be better described below, the arrangement of the elements of the storage 110 and the first and second sub-components 120, 130 within the measurement module 100 according to the invention is particularly ingenious because it makes it possible to perform infrared and fluorescence spectroscopy measurements in a reduced time on a single identical sample S by means of a single measurement module 100.

[0077] The storage container 110 for containing samples is equipped with a first wall 112 and a second wall 114 opposite to the first wall 112.

[0078] The reservoir 110 can be of any shape, as long as it includes the first wall 112 and the second wall 114 as defined above. For example, the reservoir 110 can have a parallelepiped shape. In this case, the first wall 112 and the second wall 114 can thus be formed at the level of two opposite faces of the parallelepiped. The reservoir 110 can also have a cylindrical shape. In this case, the first wall 112 and the second wall 114 thus correspond to the base of a cylinder. These are non-limiting examples.

[0079] The reservoir 110 advantageously defines a volume for containing the sample S. The volume of the reservoir 110 is advantageously about 100 mL. Furthermore, each of the first wall 112 and the second wall 114 imparts several tens of centimeters of [missing information]. 2 Preferred size: approximately 20cm 2 The illuminated surface of the grains. Importantly, despite the heterogeneity of the sample, the illuminated surface allows for measurements of a representative sample, while also allowing for a suitable measurement time (approximately 1 minute) and a suitable device size (limited volume). This avoids the use of several smaller subsamples, which not only fail to adequately represent the batch being analyzed but also require significantly longer measurement and analysis times. Therefore, the size of the storage unit is sufficient to study the amount of material representative of all products that the manufacturer wishes to know about the product's characteristics from both infrared and fluorescence spectroscopy measurements. The size of storage unit 110 also accommodates measurements via both types of spectroscopy without unduly increasing the length of the optical path between the source and detector of the first and second sub-assemblies 120, 130. In addition to these considerations, storage unit 110 can be of any size that the user of the device would deem suitable for the samples they wish to analyze.

[0080] Preferably, the reservoir 110 may also be equipped with a movable wall that makes it possible to adapt the volume of the reservoir according to the type of heterogeneous sample (granular, powdery, or doughy). The movable wall can be any wall of the reservoir 110. Therefore, it is possible to decrease / increase the depth of the reservoir, which determines the optical path of the light beam, according to which small / large particles with light absorption levels inversely proportional to their size are analyzed. If it is a first wall 112 of the reservoir, then the first wall 112 is therefore preferably movable along an axis X1 orthogonal to plane P1 passing through the first wall 112. Figure 1a In the example embodiment described, the first wall 112 extends along a substantially vertical plane P1. Therefore, the axis of movement of the movable wall 112 is a horizontal axis. According to... Figure 4a and Figure 4b and Figure 5 According to a specific implementation of the device according to the invention, the analytical device 1 includes a system 400 for holding a sample, which is configured to contain and dose a particulate powder sample in the same quantity as the dough sample.

[0081] The system 400 includes a sample storage unit 410, which can be used to store samples. Figure 5 As can be seen more clearly, the reservoir 410 includes a first glazed component 420 equipped with a first wall 422. It also includes a second glazed component 430 equipped with a second wall 432. It should be noted that the term "glazed" does not limit the scope of the invention at all, and it does not imply that any material used to manufacture the transparent wall must be glass. In fact, the material can be any other material as long as it has the same properties as the walls 122, 132 described above. The second wall 432 is separated from the first glazed component 420 by an empty volume for containing the sample. The first glazed component 420 is detachably mounted on the second glazed component 430, i.e., the first glazed component 420 can be removed from the second glazed component 430.

[0082] The retaining system 400 also includes a support block 450, a detachable part 470, and a pivot part 480.

[0083] The support block 450 makes it possible to position the holding system 400 within the measurement module 100, and in particular, to adjust the height of the storage unit 410. It includes a connector 460 and a base 454 that forms an angle / bend with the connector 460, facilitating a user grip. When the holding system 400 is inserted into the module 100, the clamping base 454 abuts against the module 100, thereby allowing the connector 460 and the removable portion 470 to extend into the module 100. The connector 460 thus itself allows the removable portion to be properly positioned within the module 100 for measurement.

[0084] The holding system 400 can be positioned within a housing disposed for this purpose within the measurement module 100, along the optical path, so that the base 454 can thus serve as a support. Alternatively, the holding system 400 can be positioned in... Figure 2a , Figure 2b The opening 150 in the middle is at a horizontal position, and this opening is used for dispensing the sample S. Therefore, the holding system 400 also functions as a barrier to prevent external light from entering the measurement module 100. In this configuration, the holding system 400 is inverted and suspended, as... Figure 4b As explained, the base 454 and the connecting portion are arranged in the opening 150 to prevent any decoupling from the holding system 400. When the holding system 400 is not positioned in this location, the cover can be used as a stop for the opening 150 during measurement.

[0085] The detachable portion 470 includes a housing 472 that receives the storage unit 410. The detachable portion 470 is preferably detachably connected to the connecting portion 460. Figure 4a In the text, the detachable part 470 is described as being in the detached position, while... Figure 4b In this context, it is described as being in the installed position. The second enamel component 430 is fixed to the removable portion 470 by being immovable within the removable portion.

[0086] The pivot portion 480 includes an opening or hole 482. The pivot portion is pivotally mounted on the support block 450. When it pivots relative to the support block 450, the pivot portion can be moved from a mounting position away from the removable portion 470 to a use position folded downwards on the removable portion 470. Figure 4b When the pivot 480 is in the use position, the opening 482 is opposite to the storage 410, which makes it possible to pass an electromagnetic beam (in this case, electromagnetic beam ES1) to that side of the storage 410 without obstructing its passage.

[0087] Furthermore, the pivot 480 includes compressible devices 486a, 486b, 488a, 488b, thereby allowing the holding system 400 to abut against the inner surface of the housing disposed in the measuring module 100 for this purpose when the pivot 480 is in the use position. Therefore, the holding system 400 is in permanent contact with the housing, particularly with the inner surface of the housing. With this configuration, the holding system 400 of the device 1 maintains the same mechanical and optical positioning from one use to another without requiring the user to demonstrate authorization or perform rigorous visual inspection. Therefore, it makes repeatable measurements possible on varying samples. This configuration is therefore preferred compared to a configuration where the holding system is positioned at the level of the opening 150.

[0088] In all cases, the sample is fixedly positioned within the measurement module 100.

[0089] For this purpose, the characteristics sought to be determined in the sample S are solid. As already mentioned, this is more specifically a sample of grains, powders, raw dough, and typically a product manufactured in the grain or dairy industry. The sample can be of any size, the only limitation being the size of the reservoir 110. That is, preferably, the size of the sample is adapted such that the amount of sample taken represents the assembly from which the sample is extracted. The sample is heterogeneous in terms of the size of its elements, as well as in terms of its shape. It may contain impurities and typically contains any foreign matter that is not strictly a dominant component within the sample. Conventionally, the whole challenge of infrared and fluorescence spectroscopy measurements can also lie in the fact that determining the proportion of such foreign matter is necessary to assess the quality of the sample S being analyzed. The sample may also be pre-crushed, such as in crisps or biscuits.

[0090] return Figure 1a The first infrared spectroscopy sub-assembly 120 includes a first excitation source 122, optical elements 140, and a transmission spectrum S for acquiring sample S. iR S i The first device 124. As mentioned above, these elements are not all grouped in a different placement than the elements that make up the second fluorescence spectroscopy subassembly, but are optimally arranged with the latter.

[0091] The first excitation source 122 is configured to emit electromagnetic radiation E in the infrared field. S1 It can also emit in the near-infrared. Preferably, it can emit polychromatic and broad-spectrum electromagnetic radiation E in the wavelength range between 700 and 1100 nm. S1 .

[0092] The first excitation source 122 emits electromagnetic radiation in the form of a beam E. S1 The electromagnetic beam ES1 is emitted to the first wall 112 of the storage device. It propagates along the optical axis X, passing through the first excitation source 122 and centered on the first source 122. Because the first wall 112 is sensitive to electromagnetic radiation E... S1 It is transparent, so the latter can pass through the first wall 112 and thus illuminate the interior of the storage 110 and the sample S if necessary. Preferably, the first source 122 illuminates the wall 112 in a uniform and collimated manner. "Collimated" means that the light from the first source has substantially parallel radiation, i.e., it is deployed without dispersion with distance.

[0093] As an example, the excitation source 122 suitable for implementing the present invention is a high-power and broadband halogen incandescent source. In addition to its ability to illuminate in an infrared field, this type of light source has high inertia, which makes it possible to limit or even eliminate flicker effects caused by fluctuations in the input current. In variations of the broadband source, several polychromatic or monochromatic sources covering the desired wavelength range can also be used.

[0094] Infrared electromagnetic radiation E S1 The interactions between the sample and the analyte are elastic in nature. They depend on the nature of the chemical bonds, forces, and axes of the molecules in the sample S being analyzed. Infrared electromagnetic radiation E S1 Only in the electromagnetic radiation E S1 Infrared spectroscopy is absorbed when the scalar product of the electric dipole moment induced during molecular vibration is non-zero. Therefore, infrared spectroscopy makes it possible to provide information about the structure and chemical composition of the sample under study.

[0095] In other words, in order to obtain quantitative information, it is used in infrared spectroscopy to perform at least two measurements so as to measure the spectrum of the sample without affecting other elements located in the optical path including the source and detector. This is also the case in the method for analyzing a sample according to the invention. In this case, it is described generally to better understand the role of the optical element 140. A first transmission spectrum S is acquired without a sample. iR (referred to as the reference spectrum), and then a second transmission spectrum S is acquired with a sample. i Reference spectrum S iR The spectrum S was collected with a sample present. i The contribution of the local environment in the sample must be measured, and must be compared with the spectrum S acquired in the presence of the sample. i Comparisons are made to extract the true signals attributable solely to the samples.

[0096] However, the reference spectrum S iR With the spectrum of the sample S i The intensity ratio between them is very high, typically around 20,000. In fact, under the same illumination conditions in terms of intensity, the reference spectrum S... iR It has very high transmittance, and has the spectrum of the sample S iThe light exhibits low transmittance. To reduce this transmittance difference, two natural solutions have been proposed. The first involves adding an absorption element to the optical path between the source and the detection device during measurements without a sample. This absorption element makes it possible to obtain similar intensities with and without a sample, but it alters the optical path between the two measurements. Therefore, the additional "component" must be accounted for in the obtained spectrum and may be removed, which can prove complex. The second solution involves altering the spectrum of the source itself by varying the light intensity between the two measurements. The resulting problem is the repeatability of the measurements.

[0097] The optical element 140 of the analytical apparatus 1 of the present invention makes it possible to avoid such constraints. In fact, the optical element 140 is diffuse and transparent to the infrared electromagnetic radiation ES1 emitted by the excitation source 122. The optical element 140 is relative to radiation E... S1 Its transparency allows it to not obstruct the radiation E S1 The propagation of electromagnetic radiation E. The diffuse characteristics of the optical element 140 itself make it possible to diffuse electromagnetic radiation E. S1 The light is deflected in all directions, and thus it is possible to reduce the intensity of the light signal reaching the first acquisition device 124, especially when the sample S is not present in the storage 110. In this case, the diffusion phenomenon is Rayleigh diffusion. The transparency and diffusion characteristics of the optical element 140 involve a number of phenomena that do not have the same range, depending on whether the storage 110 includes or excludes the sample.

[0098] according to Figure 1a and 2a In the first embodiment described, optical element 140 is positioned on the optical path between the first source 122 and the first acquisition device 124, and between the first excitation source 122 and the first wall 112 of the storage device. In other words, optical element 140 is positioned opposite both the first excitation source 122 and the first wall 112 of the storage device, but not necessarily near the first source 122 and the first wall 112 of the storage device. In this embodiment of the invention, optical element 140 more specifically constitutes the first wall 112 of the storage device. In other words, the first wall 112 and optical element 140 form only one. Similarly, in other words, optical element 140 is integrated with the storage device 110. Therefore, optical element 140 is positioned on the optical path of electromagnetic radiation ES1, and is positioned to interact with the first acquisition device 124 before reaching it.

[0099] In the absence of sample S in storage 110, the beam E is made S1Before reaching the first acquisition device 124, the beam E passes successively through the optical element 140 / first wall 112, and then through the second wall 114 of the storage. By passing through the optical element 140, it can only propagate in multiple directions and reach the first acquisition device 124 with a reduced intensity without losing information. When a sample S is present in the storage 110, the beam E... S1 Before reaching the second acquisition device 124, the beam passes successively through the optical element 140 / first wall 112, then through the sample S, and finally through the second wall 114. Therefore, even though the beam is diffused due to the optical element 140, compared to when the sample is sampled by the beam E... S1 The diffusion naturally produced by the sample as it passes through is negligible. The negligible nature of the diffusion caused by the optical element 140 during measurements with the sample depends on the sample S being analyzed. If the particle or powder sample S is naturally very diffuse, and therefore more diffuse than the optical element 140, then this is not necessarily the case for all other types of samples. Therefore, the quality of the signal measured with the optical element 140 in the presence of the sample S is not inferior to the signal measured without the optical element 140. In short, the optical element 140 makes it possible to acquire the reference spectrum S of the sample under the same conditions of illuminating the first excitation source 122 during the acquisition of two spectra. iR and spectrum S i This makes it possible to freely choose the data collection device.

[0100] As illustrated, the optical element 140 does not need to be positioned parallel to the first wall 112. Preferably, the optical element 140 produces isotropic diffusion in all directions. Therefore, as long as it is located in the optical path, it can be tilted relative to the optical axis X without blocking the infrared electromagnetic beam E. S1 It propagates around the optical axis X, while simultaneously performing its primary function of diffusing light. For example, optical element 140 can be manufactured by frosting glass.

[0101] according to Figure 1b and 2b In the second embodiment described, the optical element 140 and the first wall 112 of the storage can be separated. In this configuration, the optical element 140 is presented as an element different from the first wall 112. It may be located at a distance from the storage 110 and stabilized by means of a support, but this is not mandatory. It may also be bonded to the first wall 112 of the storage, rather than serving as the first wall 112. Regardless of the configuration considered, i.e., whether the optical element 140 constitutes the first wall 112 or is separate from the first wall 112, it is important within the scope of the invention that the optical element 140 in the electromagnetic beam E S1 Position the electromagnetic beam E before reaching the first acquisition device 124. S1 On the optical path.

[0102] In addition to the optical element 140, the first sub-assembly 120 may include the electromagnetic beam E S1 A collimating lens 126 is provided in the optical path for the excitation source 122. Preferably, the collimating lens 126 is located between the excitation source 122 and the optical element 140, which is integrated with or separate from the storage device 110. The collimating lens 126 makes it possible to collimate the electromagnetic beam E from the excitation source 122. S1 The parallel arrangement ensures uniform illumination of the interior of the storage unit 110, especially the sample S. The information obtained from the measurements is both more qualitative and quantitative.

[0103] In variations of the first and second embodiments of the present invention, the optical element 140 can cause the electromagnetic beam E S1 It is possible to diffuse the radiation while simultaneously making it possible to collimate it. In this case, collimating lens 126 is not necessary because optical element 140 acts as the collimating lens by fulfilling its first function, which is to diffuse the radiation from the first excitation source 122. For example, such an element can be manufactured by frosting the collimating lens.

[0104] Furthermore, as described above, the first sub-component 120 includes a first device 124 for acquiring transmission spectra. In this respect, the first acquisition device 124 makes it possible to detect electromagnetic signals emitted in the visible, near-infrared, and infrared fields, particularly at wavelengths between 750 and 2500 nm. As seen in the sections above, the use of optical elements 140 allows for freedom in the selection of the acquisition device.

[0105] In a preferred embodiment of the invention, the first acquisition device 124 is a single charge transfer detector or charge-coupled device (CCD) sensor. Detectors based on complementary metal-oxide-semiconductor (CMOS) sensors, photodiodes, or any other detection devices known to those skilled in the art may also be used. In practice, it is preferred to use the detector in conjunction with a monochromator. The monochromator makes it possible to select the desired spectral fields(s), i.e., to adapt the signal collection to the analysis under consideration. For example, a monochromator(s) could be a chromaticity filter(s) or a spectrometer.

[0106] The first acquisition device 124 is advantageously aligned along the optical axis X with the excitation source 122, the diffuse and transparent optical elements 140, and the storage device 110. In other words, these elements are all on the optical path. The first acquisition device 124 has a field angle centered on the optical axis X. Nevertheless, it is important in this case that the first acquisition device 124 is arranged such that when the sample is exposed to the infrared beam E... S1 Detecting reference signals S in the case of illumination emissioniR and (various) signals S i .

[0107] From the viewpoint of the infrared spectroscopy sub-component 120, if the arrangements that enable infrared spectroscopy measurements, as described above, are ingenious (because they provide diffuse and transparent optical elements 140), they are even more ingenious because they do not hinder fluorescence spectroscopy measurements performed on the same sample S. This will be described in more detail below.

[0108] The second fluorescence spectroscopy sub-assembly 130 includes a second excitation source 132 and a fluorescence signal S for acquiring the sample S. f1 S f2 The second device 134. The second excitation source 132 is configured to emit electromagnetic radiation E in the ultraviolet field. S2 It can further emit in the visible field. According to a preferred embodiment, it can emit monochromatic radiation with wavelengths between 250 and 550 nm. Examples of a second excitation source 132 that can be used in the analytical apparatus 1 according to the invention include at least one light-emitting diode (LED) emitting wavelengths of 280 nm, 340 nm, 385 nm, or 420 nm. The advantage of LED sources is their strong and uniform illumination capability. In addition, they have a long lifespan.

[0109] Preferably, the number of excitation sources 132 can be adjusted according to the size of the surface to be analyzed. When using multiple second excitation sources 132, such as... Figure 1a and 1b As shown, a support 136 can therefore be provided, which is configured to receive the source 132, and thus hold each source on a single support. In this respect, Figure 3 In the example of the embodiment described, the support 136 includes an assembly portion 1360 and a support portion (not described) that makes it possible to stabilize the assembly portion 1362. The assembly portion 1360 includes a plurality of housings 1362 arranged circularly around a central opening 1364 of the support and in which the second source 132 can be secured. Specifically, the housings 1362 are appropriately sized to receive the second source 132 and include means for securing the source 132, making it possible to retain the source, for example, by screws and / or nuts. Preferably, the assembly portion 1360 is removable so that it can be detached from the support 136.

[0110] In one variant, a broadband source can also be used as a second excitation source 132, which emits electromagnetic radiation E in an ultraviolet field. S2 And a monochromator combined with such a source. In this configuration, the broadband source is polychromatic in nature, and it is necessary to associate it with a monochromator in order to obtain a broadband electromagnetic beam E S2Choose a narrower wavelength range or wavelength. This configuration is more complex than the previous one, which uses an LED source. An example of a broad-spectrum source emitting in the ultraviolet field is a deuterium lamp, which emits at wavelengths between 180 nm and 370 nm in the ultraviolet field.

[0111] The second excitation source 132 will generate an electromagnetic beam E S2 The second wall 114 of the storage is transmitted to the opposite side of the storage 110, according to the first and second embodiments ( Figure 1a , 1b (2a, 2b) Diffusing and transparent optical elements 140 are positioned on opposite sides of the memory. The second excitation source 132 can be eccentric relative to the optical axis X. When multiple sources 132 are used, each source can be eccentric relative to the optical axis X, such as... Figure 4a As explained in section 4c, the source 132 is advantageously tilted in the central direction of the second wall 114, which allows the light source to uniformly and properly illuminate the second wall 114. Importantly, in this case, the second source 132 is positioned so as not to obstruct the acquisition of infrared and fluorescence spectra.

[0112] The second source 132 emits an electromagnetic beam E toward the second wall 114. S2 This fact is neither an anecdote nor a simple choice of arrangement. As mentioned earlier in the detailed description of the invention, the problem of the invention is to provide an apparatus 1 that makes it possible to perform infrared and fluorescence spectroscopy measurements on the same sample S in a reduced time, without having to perform the measurements in separate sub-modules, and therefore without having to divide the sample into two parts or transfer it from one module to another. This choice of arrangement makes it possible to perform infrared and fluorescence spectroscopy measurements on the same sample without interference from the elements of the first sub-component 120 necessary for infrared spectroscopy measurements.

[0113] In fact, the very low intensity of fluorescence relative to the source intensity makes it highly sensitive to diffusion, which itself depends on the physicochemical properties of the sample. Even low-intensity diffusion can disrupt, i.e., interfere with, the fluorescence signal. If it does not impede the extraction of quantitative data, the component resulting from spectral diffusion can significantly complicate the extraction of useful data for analysis and / or necessitate the use of filters, which currently have a very limited effect on the reduction in the light share caused by diffusion in the final spectrum.

[0114] Because it is positioned between the first excitation source 122 and the first wall 112 of the storage device, the diffuse optical element 140 can function for infrared spectroscopy measurements without interfering with fluorescence spectroscopy measurements. In fact, fluorescence spectroscopy measurements only require illumination of the storage device 110 on one side of the second wall 114 (i.e., the side opposite to the diffuse optical element 140), if necessary. Therefore, the electromagnetic beam E emitted by the second excitation source 132... S2 No interaction occurs between the optical element 140 and the storage 110 and sample S and the first excitation source 122 and the second excitation source 132. The ingenious arrangement of the components of module 100 and the optimal illumination orientation of the storage 110 and sample S with respect to the first excitation source 122 and the second excitation source 132 makes it possible to perform two types of measurements without one measurement “interfering” with the other. Thus, the challenge of the invention is achieved: the ability to perform infrared spectroscopy measurements and fluorescence spectroscopy measurements on the same sample within a reduced time frame. This arrangement also makes it possible for the second sub-component 130, necessary for fluorescence spectroscopy measurements, to not interfere with infrared spectroscopy measurements.

[0115] It should be noted that if, in the first and second embodiments of the present invention, the diffuse optical element 140 is located between the first excitation source 122 and the first wall 112 of the storage device, those skilled in the art can consider another positioning, provided that the optical element 140 is positioned so as not to obstruct fluorescence spectroscopy measurements and is positioned between the first excitation source 122 and the first acquisition device 124. The optical element 140 is positioned so as not to obstruct fluorescence spectroscopy measurements, provided that it does not interfere with the electromagnetic beam E emitted by the second acquisition device 134. S2 Furthermore, when exposed to such a beam of light, it does not interfere with the fluorescence signal emitted by the sample. Taking the above constraints into account, the optical element 140 is positioned between the first source 122 and the first acquisition device 124, provided that it is positioned such that the radiation E emitted by the first source 122... S1 It diffuses light without preventing it from being detected by the first acquisition device 122 during measurements with and without samples.

[0116] Therefore, in another embodiment of the invention, the optical element 140 may also be positioned between the second wall of the storage 114 and the first acquisition device 124, in the electromagnetic radiation E emitted by the second excitation source 132. S2 Outside the optical path, and in the electromagnetic radiation E emitted by the second excitation source 132 S2 The solid angle used to collect the fluorescence signal emitted by sample S when exposed. In this embodiment, the second wall 114 of the storage cannot be made of optical element 140, as this would necessarily hinder fluorescence spectroscopy measurements. Figure 1c An example of a device 100 corresponding to such an implementation is explained.

[0117] Furthermore, the second wall 114 of the storage device is sensitive to electromagnetic radiation E emitted by the second source 132. S2 It is transparent, making the radiation E S2 It can penetrate the second wall 113, thereby illuminating the interior of the storage device 110 and the sample S. Furthermore, the second wall 114 of the storage device is sensitive to electromagnetic radiation E. S2 It is anti-reflective. The anti-reflective properties of the second wall 114 make it possible to increase the proportion of light transmitted through the second wall 114 and reaching the sample S. Therefore, this makes it possible to improve the detection of the fluorescence signal, which can be shown to be relatively low, thus making it possible to optimize fluorescence spectroscopic measurements.

[0118] Furthermore, the second wall 114 of the storage device is affected by the infrared electromagnetic radiation E emitted by the first excitation source 122. S1 It is also transparent to infrared electromagnetic radiation re-emitted by the sample S or its neighboring environment.

[0119] In this regard, as already mentioned above, the support 136 also includes a central opening 1364. The opening 1364 is central because it leaves a wide, empty area without material around the optical axis X, making it possible for electromagnetic radiation generated by infrared and fluorescence spectroscopy measurements to pass through. The opening 1364 is sized to allow as much light beam as possible to pass through, making it possible to collect the maximum number of signals for infrared spectroscopy measurements. In the example of the illustrated embodiment, the central opening 1364 is circular, but this is not mandatory. The central opening 1364 can take any other shape, as long as it does not obstruct the collection of infrared signals.

[0120] The second acquisition device 134 is dedicated to fluorescence spectroscopy measurements. In this respect, the second acquisition device 134 makes it possible to detect electromagnetic signals emitted in the ultraviolet and visible fields, and more specifically, electromagnetic signals emitted at wavelengths between 200 and 550 nm. The second acquisition device 134 can be a CCD sensor, a CMOS sensor, a photodiode, or any other detection device known to those skilled in the art. Preferably, the detector is used in conjunction with a monochromator, such as one or more chromaticity filters or a spectrometer.

[0121] The second acquisition device 134 is advantageously angled α to the optical axis X. In other words, the axis X' passing through the second acquisition device 134 and the intermediate plane, and substantially perpendicular to the second wall 114 of the storage, forms an angle α with the optical axis X. Therefore, the axis X' is the axis with the second acquisition device 134 relative to the optical axis X. Consequently, the second device 134 is not optically aligned with the other elements of the module 100, namely the first excitation source 122, the optical element 140, the storage 110, the second excitation source 132, and the first acquisition device 124. This is derived from the fact that the second source 132 emits electromagnetic radiation E on either side of the optical axis X. S2 Only the electromagnetic radiation portion located in the field angle around the axis X′ of the second acquisition device 134 is detectable.

[0122] The illumination of the second wall 114 by the second source 132 produces specular reflection, which remains significant despite the anti-reflection treatment applied to the second wall 112 of the storage device. Reflection is called specular reflection when incident radiation is reflected in a given direction in a manner similar to a mirror reflecting a beam. This can lead to saturation of the detection device because a large portion of the electromagnetic radiation is still reflected specularly in the direction of the optical axis X. In this case, the second excitation source 132 emits electromagnetic radiation E towards the second wall. S2 The second wall 114 is passed through by the optical axis X, which inevitably generates specular reflection. An angle α is chosen such that the second acquisition device 134 is not directly located on the optical path of the beam reflected specularly by the second wall 114 of the storage device, while maintaining the maximum fluorescence emission of the sample in an isotropic manner. For example, angle α is taken to be equal to 10°.

[0123] Measurement modules 100, as described above, make it possible to group elements into a single module, each element enabling both infrared and fluorescence spectroscopy measurements, without having to divide the sample into two parts and therefore perform two separate analyses spatially or even temporally, or without having to perform the two types of measurements continuously over time. If the device 1 according to the invention makes it possible to measure the same sample S using both types of spectra within a time frame of several minutes, it is also configured to process the resulting data.

[0124] In this respect, in addition to the measurement module 100, the device 1 according to the invention also includes a processing module 200 connected to the measurement module 100. The processing module 200 can be any type of electronic or computerized processing device, such as a computer, smartphone, or any similar device with a control screen at the terminal, a USB stick, a mobile memory card, or any other similar technology. Preferably, the processing module 200 is an embedded PC.

[0125] The processing module 200 is connected to the single measurement module 100 of the analysis device 1 via a communication network 300. The communication network 300 makes it possible to connect the processing module 200 to the measurement module 100. For example, the communication network 300 is a local network such as a wired network, Bluetooth network, Wi-Fi network, or Ethernet. In any case, the communication network 300 is configured to transmit information between the processing module 200 and the measurement module 100 of the device 1. Since the measurement module 100 is unique, there is no interface between measurement and processing.

[0126] The processing module 200 includes a processor 220 and a memory 240.

[0127] The memory 240 is configured to receive and store data transmitted by the communication network 300. This data may include any type of information measured by the measurement module 100, such as infrared E emitted by the sample. S 1 and fluorescence E S2 The wavelength of the radiation, the intensity measured from these radiations, or the corresponding electromagnetic spectrum.

[0128] Processor 220 is configured to analyze and / or process data obtained through infrared spectroscopy and fluorescence spectroscopy. In this regard, software for processing this data can be installed on the processor to automate the processing of the data in real time. Importantly within the scope of this invention, processor 220 is capable of processing data sequentially from infrared spectroscopy measurements and those from fluorescence spectroscopy measurements over time frames of several minutes to extract evaluation factors and / or criteria from the sample S under study. The operations performed by processor 220 will be described in more detail below relative to the methods used to analyze sample S.

[0129] In fact, the present invention also relates to a method for analyzing a sample S, which is implemented by means of an analytical device 1 such as those described above. The method according to the present invention includes the following steps.

[0130] During the first step a), the transmission spectrum S is acquired from the sample S using the first infrared spectroscopy sub-component 120. i If such a measurement could theoretically be performed directly, then without a reference infrared spectrum S... iR Without additional measurements (also known as the spectrum without a sample), it is impossible to accurately quantify the phenomenon that varies from sample to sample, i.e., the transmittance of the sample. As described above, the reference spectrum S iR The measurement makes it possible to quantify the contribution of the local environment to the sample transmission spectroscopy measurement.

[0131] Step A) of the method according to the invention advantageously includes sub-steps Aa), Ab), Ac), Ad), and Ae), steps Aa) and Ab) being related to the reference spectrum S.iR The measurements are related to and therefore performed with a sample to be analyzed, and steps Ac) to Ae) are related to the spectrum of the sample S. i The measurement is related to and therefore can be performed with a sample to be analyzed.

[0132] During sub-step Aa), by means of electromagnetic radiation E generated by the first source 122 S1 To illuminate storage device 110. Electromagnetic beam E S1 Before reaching the first acquisition device 124, the electromagnetic beam passes sequentially through the optical element 140, and then through the first wall 112 and the second wall 114 inside the storage device. Therefore, the electromagnetic beam E... S1 The path along the optical axis X is described. The interior of the storage device is empty; it does not contain any sample. Furthermore, storage device 110 is kept filled with air and other elements present in the air, which can absorb and reflect some electromagnetic radiation E. S1 .

[0133] It should be noted that if the first wall 112 of the storage is composed of optical elements 140, then the light beam E S1 Therefore, the electromagnetic beam E will pass sequentially through the optical element 140 inside the storage and the second wall 114 of the storage before reaching the first acquisition device 124. It should also be noted that if the collimating lens 126 is optionally inserted between the first excitation source 122 and the optical element 140, the order in which the beam passes through the different elements will be affected together. Furthermore, it should be noted that in embodiments where the second excitation source 132 includes multiple sources supported by the support member 136, the electromagnetic beam E... S1 It must pass through the opening 1364 of the support located on the optical path.

[0134] During sub-step Ab), the reference transmission spectrum S is measured. iR .

[0135] During substep Ac), the memory 110 of the sample S to be studied is filled. If a comparative measurement must be performed between several samples, the memory 110 will be systematically filled with the same amount of sample.

[0136] During sub-steps Ad) and Ae), steps Aa) and Ab) are repeated, except that, in this case, the sample S to be studied is placed in storage 110. At the end of this second acquisition sequence, the transmission spectrum S of the sample is obtained. i .

[0137] The data collected during step A), especially the reference transmission spectrum S iR and the S of the sample iThey are then analyzed and / or processed by processor 220. Preferably, they are stored in the memory 240 of the processing module. This will return to the following.

[0138] In step B of the method according to the invention, the fluorescence spectrum S of the sample S f1 S f2 This was obtained using the second fluorescence spectroscopy sub-component 130. The sample S involved is strictly the same sample analyzed during step A). ​​In other words, it is not a sample divided into two types of measurements. Furthermore, it must be noted that step B) does not necessarily need to be performed after step A). ​​It can also be performed before or after step A).

[0139] Step B) of this method includes sub-steps Ba), Bb), Bc), and Bd) described below. During a constant integration time, when fluorescence spectroscopy measurements are performed over an extended wavelength range, for example, between 250 nm and 650 nm, the signal intensity may be available in a portion of this wavelength range, while it may be unavailable and saturate the acquisition device in another portion. This arises from the dynamic range between diffuse and fluorescence. In practice, a fluorescence spectrum always includes the wavelength range on which diffuse is measured and the wavelength range on which the fluorescence signal itself is measured. However, the maximum intensity of the measured signal from diffuse is greater than the maximum intensity of the signal from fluorescence. The intensity ratio measured between these two measurements may be approximately 100. However, both components of the signal are equally important for the physicochemical analysis of the sample. Therefore, it is desirable to return them to similar intensity levels. During the first sub-step Ba), electromagnetic radiation E emitted by the second excitation source 132... S2 The electromagnetic beam E emitted by the first source 132 is used to illuminate the storage device 110 and the sample S, given the arrangement of the elements of the second sub-assembly 130. S2 It passes sequentially through the second wall 114 of the storage unit, and then through the sample. Electromagnetic beam E S2 The interaction with sample S thus generates a fluorescence signal that varies depending on sample S.

[0140] During the second sub-step Bb), the first fluorescence spectrum S of the sample S is acquired simultaneously with step Ba) at a predetermined integration time t1 using the second acquisition device 134. f1The determination of this integration time may require prior measurements of the sample S under study in order to optimize the signal share due to diffusion or the signal share due to fluorescence. The signal is considered optimized when the signal-to-noise ratio is high enough to allow extraction of the desired parameters. Whatever it is, and as mentioned in the preceding sections, given the contributions of these two phenomena (i.e., diffusion and fluorescence) in the final spectrum, the signal measured by the second acquisition device 134 proves unusable over a portion of this wavelength range.

[0141] During the third sub-step Bc) and the fourth sub-step Bd), sub-steps Ba) and Bb) are repeated, but this time, an optimized integration time t2 is selected to measure another component of the signal, either the signal share due to diffusion or the signal share due to fluorescence whose integration time was not optimized during sub-step Bb). From these steps, the second fluorescence spectrum S is obtained. f2 .

[0142] For example, it is thought that attempts are being made to measure at λ1 and λ n The fluorescence signal is within the wavelength range of λ1 to λ2. At integration time t1, the fluorescence signal is within the range of λ1 to λ2. m It is unavailable on the top, but available on the rest of the range, i.e., λ. m+i To λ n , where i is the step size between measurements. In S f2 During the acquisition sequence, if the fluorescence signal is in the range λ1 to λ m If the unavailable mode is low signal-to-noise ratio, then an integration time t2 greater than t1 will be selected, or conversely, if the fluorescence signal is in the range λ1 to λ2... m If the unavailable mode is the saturation of the second acquisition device 134, then an integration time t2 less than t1 will be selected.

[0143] Therefore, at the end of the second step B) of the method according to the invention, two fluorescence spectra S are obtained. f1 and S f2 Collect these two fluorescence spectra S f1 and S f2 These two fluorescence spectra are then processed by processor 220. It should also be recalled that the reference infrared spectrum S associated with the infrared spectroscopic measurements... iR and the infrared spectrum of the sample S i It is also collected and processed by processor 220.

[0144] Although in the above embodiment, the fluorescence spectroscopy measurement step B) is performed after the infrared spectroscopy measurement step A), step B) can also be performed before step A) without any bias, since these steps are independent.

[0145] During the third step C) of the method according to the invention, data obtained by infrared spectroscopy and fluorescence spectroscopy are analyzed by means of processing module 200, and processor 220 is configured to determine at least one indicator characterizing the sample from the analyzed data. Step C) of the method according to the invention is a step performed by a computer. The term "computer" has a broad meaning and means any device equipped with a processor and capable of performing tasks according to programmed commands. Whatever it is, from step C), at least one indicator characterizing the sample S under study is obtained. In this respect, it can be stated without a doubt that this step is preferably performed after steps A) and B).

[0146] Next, the processing of the infrared and fluorescence spectra obtained from steps A) and B) will be discussed below.

[0147] During the first sub-step Ca), from the reference spectrum S iR and the S of the sample i Determine the final transmission spectrum S of sample S. if In this regard, median smoothing can be applied first at one or more (±1) pixels to remove the reference infrared spectrum S. iR and the S of the sample i The defective pixels in the sample. Then, secondly, this is the spectrum S of the removed sample. i The contribution of the local environment. Therefore, the sampled signal S is calculated. i With reference signal S iR The ratio between them. At this stage, it must be noted that the intensity ratio between the two spectra is typically 1000. Therefore, the use of diffuse optical elements makes it possible to measure S without a sample. iR With a sample measurement S i Divide the intensity ratio between the two by 20. Therefore, the final transmission spectrum S is obtained. if The resulting spectrum can also be normalized to return it to a percentage value.

[0148] During the second sub-step Cb), the spectrum S f1 and S f2 (Consider the example above) Form the final fluorescence spectroscopic spectrum of sample S. This spectrum will be referred to below as the "final spectrum" S. ff The cascading of these spectra is performed as follows: 1) from the spectrum S measured for this purpose f1 and S f2 2) Recover the optimized spectrum from the diffuse signal in the image, and 3) Calculate another spectrum S for this purpose. f1 or S f2The optimized spectrum is recovered from the fluorescence signal, and 3) by combining these optimized diffuse and fluorescence spectra, the final spectrum S is obtained. ff The final spectrum exhibits a good signal-to-noise ratio for the spectral components caused by diffusion as much as those caused by fluorescence. Therefore, across the entire spectrum, particularly in the portion corresponding to the fluorescence component, the signal-to-noise ratio of the spectral shares due to diffusion and those due to fluorescence returns to a value of 100, which is greater than the ratio of 10 without processing. Spectrum S f1 and S f2 The wavelength range extending from it is described below.

[0149] Continuing with the previous example, corresponding to λ m+i To λ n The optimal measurement of fluorescence spectrum S performed within the wavelength range between f1 Therefore, it can be associated with the region corresponding to λ1 to λ m The optimal measurement of the diffuse spectrum S performed within the wavelength range between f2 Cascade—i is a natural integer corresponding to this step size. The resulting final fluorescence spectrum S ff From λ1 to λ n The spectrum extends between and exhibits good quality in both the spectral portion associated with the signal share from diffuse and the spectral portion associated with the signal share from fluorescence. For example, due to the cutoff wavelength defined by the LED, cascading also makes it possible to cascade spectra that can only be measured with different sources 132. The final sub-step will include processing the resulting final spectrum S. ff Perform Gaussian smoothing.

[0150] In fact, spectrum S f1 and S f2 One of the spectra corresponds to the "diffuse" component of this fluorescence spectrum and extends over a wavelength range of approximately 250 nm between the cascade wavelengths, while spectrum S... f1 and S f2 Another spectrum corresponds to the "fluorescence" component of this fluorescence spectrum and extends over a wavelength range between cascaded wavelengths, essentially 650 nm and even greater than 650 nm. This is located at the excitation wavelength (i.e., the electromagnetic radiation E0). S2 The cascade wavelength (beyond the excitation wavelength) is the minimum value in the wavelength range that is close to the excitation wavelength. In the case of grain measurements, the cascade wavelength is equal to the excitation wavelength added between 10 and 20 nm.

[0151] Because of this coupled measurement system, acquiring fluorescence emission and infrared transmission spectra on the same subsample makes it possible to group all the spectral information (and some supplementary information) provided by these two optical techniques to enrich the knowledge of the heterogeneous sample being analyzed. Due to the implemented device, the coherence between the information acquired by these two infrared and fluorescence techniques (because these spectra correspond to the same sample) ideally makes it possible, and for the first time, to collect them to perform the merging of information contained in each of these spectra.

[0152] It is particularly important to emphasize that, in the existing method (referred to as the reference method), there are no third and fourth sub-steps Bc) and Bd). Fluorescence spectra are acquired using only a single operating parameter. f1 The result is that either the signal component due to diffusion is optimized, or the signal component due to fluorescence is optimized, or neither is optimized. Therefore, according to this reference method, because no spectrum S is acquired... f2 Therefore, the final fluorescence spectrum S f Corresponding to spectrum S f1 .

[0153] In addition, based on the methods described above for cascade spectroscopy, other methods can be implemented to utilize information from these fluorescence and infrared spectra; several methods are possible.

[0154] However, before anything else, the infrared and fluorescence emission transmission spectra must first be processed and then combined. This is preprocessing.

[0155] Fluorescence spectra are processed to separate the diffuse portion of the fluorescence spectrum, thereby obtaining a pure fluorescence spectrum. Several methods can be considered for this purpose:

[0156] • If this (diffuse) spectrum does not overlap with the fluorescence spectrum, then the diffuse spectrum is truncated.

[0157] • Modeling of diffuse patterns and removal of modeled diffuse patterns

[0158] • Use chemometric tools that make it possible to distinguish between diffuse and pure fluorescence signals, such as ICA (independent component analysis).

[0159] Thus, for each measurement, as many fluorescence emission spectra as the excitation (LED) wavelength, as well as infrared transmission spectra, were achieved.

[0160] There are two main approaches to coupling signals. They differ in the following order: on the one hand, they couple information, and on the other hand, they reduce this information from thousands of variables to one to twenty without losing useful information. Different calibration or classification models can apply this reduction to these new variables.

[0161] Therefore, the two main methods are as follows:

[0162] A low-level approach couples reduced information or fractions from the decomposition of each spectrum. Possible variable reduction methods are shown below. This yields a finite number of variables containing almost all the initial information. These variables can then be modeled using different calibration or classification algorithms.

[0163] Advanced methods include coupling the spectra themselves before performing variable reduction steps. The best way to couple spectral information is through cascaded spectroscopy. Various variable reduction techniques can then be applied, such as principal component analysis in this case. Therefore, reduced information combining these two techniques, such as multilinear regression or classification, is introduced into the calibration model.

[0164] Now, we will explore the various technologies that can be applied to each of these operations.

[0165] Cascaded: The spectrum is organized end-to-end, preferably with each fluorescence emission spectrum following an increasing excitation wavelength, followed by an infrared transmission spectrum. In this case, several precautions will be taken:

[0166] To give each spectrum the same weight within the set, the spectra must be normalized and thus assigned similar intensities. For example, normalization can be achieved by area, by the standard deviation of the spectrum followed by centering, or by normalization by the maximum value, causing the intensity to vary between 0 and 1.

[0167] Then, it must be ensured that no breaks occur between the signal at the last wavelength of spectrum N-1 and the signal at the first wavelength of the subsequent spectrum N. Different techniques are possible to achieve this, such as forcing the value to zero if the portion of the spectrum in question does not contain information. Regardless, it is essential to smooth the spectrum to obtain a regular signal.

[0168] These are the methods seen above.

[0169] Information Reduction: This reduction of information from spectral variables is also known as spectral decomposition. Since each intensity at each measured wavelength corresponds to a variable, there is a very high degree of redundancy among all these highly correlated variables. Therefore, the idea is to extract independent information whose sum covers all the initial information contained in the spectrum.

[0170] The most known decomposition method is principal component analysis, which ensures that each new variable, called a principal component, forms a vector orthogonal to the system composed of the other principal components. The number of components is determined by the model's ability to explain all spectral variance. However, from a certain level of decomposition, this variance now only contains noise.

[0171] In the case of multipath structures, such as 3D fluorescent structures, multipath techniques such as PARAFEC (PARALellFACTor analysis) can be applied. This is about identifying individual 3D structures, factors, or even individual fluorophores, which are grouped together to contain all the collected fluorescence.

[0172] calibration

[0173] Regardless of the spectral decomposition technique, a single or cascaded new variable is typically obtained, called a single factor or principal component, in a limited number, approximately 10 to 20. Therefore, each sample is represented by a linear combination of these variables and by specific weights for each of them. These weights are usually named as fractions.

[0174] Echi = a i1 x V1+a i2 x V2+…a in x V n +constant

[0175] Where a in It is the weight of each variable, while V n It is the number of variables obtained during the decomposition.

[0176] Therefore, the score is used to characterize sample i for this decomposition.

[0177] Therefore, during calibration, only these fractions of the responses of interest are used, which are sought to be predicted by spectroscopic measurements.

[0178] The most common calibration methods are PCR (principal component regression) or MLR (multiple linear regression) for linear pattern calibration.

[0179] Another linear regression method, PLS (Partial Least Squares), has the specificity and advantage of reducing the cascaded spectrum in the new variable while considering its correlation with the response to be calibrated and predicted. Therefore, reduction and calibration are performed in a single step.

[0180] Similarly, nonlinear methods can be used as random forests or nearest neighbor techniques, or even neural networks.

[0181] Example of an embodiment of the analysis device 1 according to the present invention

[0182] Regardless of the examples considered below, processing module 200 is a computer, but it can be any device equipped with processor 220, such as the devices already defined in the preceding sections. Regarding communication network 300, it is wired. That is to say, it can be of any other nature.

[0183] The components of the measurement module 100, which have already been described in detail below, are of interest.

[0184] In an example of an embodiment of analytical apparatus 1, the optical element 140 comprises an enamel wall, designated by Edmund Optics under reference 84479, and equipped with a diffuser, also designated by Edmund Optics under reference 83420. The diffuser is composed of high-quality frosted glass with a roughness sufficient to produce diffusion. The glass is frosted using a frosting method, which allows for uniform diffusion across the entire surface.

[0185] In an example of an embodiment of the analysis device 1, the first excitation source 122 comprises a high-power, broadband halogen incandescent lamp assigned by Newport under reference number 6335. It emits infrared electromagnetic radiation between 750 nm and 2500 nm.

[0186] In an example of an embodiment of the analysis device 1, the collimating lens 126 is assigned by Newport under reference KBX139.

[0187] In an example of an embodiment of the analytical apparatus 1, the second excitation source 132 comprises a plurality of LEDs. Seven of the first LEDs (a total of four) emit electromagnetic radiation at a wavelength of 275 nm and are distributed by HTDS under reference number CUD7GF1B. The second LED emits electromagnetic radiation at a wavelength of 338 nm and is distributed by HTDS under reference number CUD4AF1B. The third LED emits electromagnetic radiation at a wavelength of 285 nm and is distributed by HTDS under reference number CUN8AF1B. The fourth LED emits electromagnetic radiation at a wavelength of 420 nm and is distributed by Roithner under reference number LED420-01. All LEDs can be mounted to a factory-manufactured support 136.

[0188] In an example of an embodiment of the analysis device 1, a calibration lens may also be used in combination with the second source 132. Such a collimating lens is assigned by Edmund Optics with reference number 49556.

[0189] In an example of an embodiment of the analysis device 1, the first acquisition device 124 consists of an Optoprim-assigned avaspec-2048XL spectrometer.

[0190] In an example of an embodiment of the analysis device 1, the second acquisition device 134 consists of an Optoprim-assigned avaspecULS-2048L spectrometer.

[0191] In an example embodiment of analysis device 1, storage 110 includes a sample detector window referenced by Thorlabs as WW10530-B. Storage 110 may also include a presence detector referenced by Mouser as VCNL4040M3OE. Such a device makes it possible to improve the automation of the analysis method according to the invention.

[0192] In an example of an embodiment of analytical apparatus 1, storage 110 may be equipped with a temperature sensor. The temperature sensor may consist of a window that acquires the temperature assigned by Thorlabs under reference number WW70530. Another suitable temperature sensor is sold by Mouser under reference number MLX90614ESF ACC000SP. Knowledge of temperature is extremely useful for controlling the development of samples.

[0193] Example of actual implementation of the method of the present invention

[0194] refer to Figure 6a The original spectrum (solid line) obtained during step B) using the method according to the invention is compared with the original spectrum (dashed line) obtained by fluorescence spectroscopy using a reference method known in the prior art. The relevant sample is barley, presented in grain form. The excitation wavelength used for these measurements has been fixed at 340 nm. Figure 6a As can be seen, the signal-to-noise ratio of the original spectrum obtained by the reference method is significantly lower than that of the original spectrum obtained by applying the method according to the invention during step B).

[0195] Figure 6b The results of applying a Gaussian-type digital filter are shown, the purpose of which is to filter out electronic noise present in the signal during step B) by applying the original spectrum (solid line) obtained during step B) by applying the method according to the invention and by means of a reference method known in the prior art by fluorescence spectroscopy (dashed line).

[0196] also, Figure 6c The excellent reproducibility of fluorescence measurements performed during implementation of the method of the present invention on the same sample is demonstrated. Despite previous applications of digital filters, it is significantly superior to using a reference method ( Figure 6d The repeatability is achieved by performing the same measurements. The significant advantage of measurement repeatability is explained by optimizing the signal-to-noise ratio of the spectrum on all spectral components allowed by the implementation of the method according to the invention at the acquisition level.

[0197] exist Figure 6e and 6fAs can be seen from the implemented method, this results in a significant difference in residue relative to the average spectroscopic measurement. By applying the method of the present invention, on the one hand, the variation in residue is smaller, and on the other hand, there is less overlap between residues in each repetition.

[0198] refer to Figures 7a to 7f As can be seen, the same conclusion applies when the excitation wavelength is 385nm.

[0199] The following table summarizes Figure 8a , 8b The results explained in section 9. Figure 8a and 8b In this study, 204 flour samples were measured on the same device, using an infrared module on one side and a fluorescence module on the other (separately from existing methods). The figure below shows the calibration regression obtained by connecting the values ​​of each sample measured by the reference method on the horizontal axis and connecting the predicted values ​​in cross-validation obtained by least-squares regression in infrared fluorescence or multiple linear regression in fluorescence spectroscopy on the vertical axis, the latter itself constructed from PARAFAC decomposition scores.

[0200] [Table 1]

[0201]

[0202] abbreviation:

[0203] -RMSEC stands for "Root Mean Square Error of Calibration".

[0204] -RMSEVC stands for "Root Mean Square Error of Cross-Validation", and

[0205] -RMSEP stands for "Root Mean Square Error of Prediction".

[0206] Table 1 illustrates the significant improvement in calibration error, the degradation of external predictions when both techniques are used alone, and the degradation observed in cross-validation when coupled. However, this can be represented by a slight over-modeling during calibration.

[0207] In all cases, the performance of external predictions was improved by more than 3 times due to the coupling of infrared spectroscopy and fluorescence spectroscopy measurements.

[0208] The embodiments mentioned in the above figures are merely possible examples of the present invention and are not intended to be limiting. Rather, the present invention includes variations of embodiments and designs that are within the scope of those skilled in the art.

Claims

1. An apparatus (1) for analyzing a heterogeneous sample (S), the apparatus (1) being characterized in that it comprises: - a measurement module (100) comprising: - a reservoir (110, 410) configured to contain the heterogeneous sample (S) and equipped with a first wall (112, 422) and a second wall (114, 432) opposite the first wall, a first infrared spectroscopy sub-assembly (120) comprising: a first excitation source (122) configured to emit electromagnetic radiation (E S1 ) in the infrared and / or near-infrared field to the first wall (112, 422) of the reservoir, the first wall (112, 422) being transparent to infrared electromagnetic radiation (E S1 ); and first acquisition means (124) for acquiring a transmission spectrum (S iR , S i ), a second fluorescence spectroscopy sub-assembly (130) comprising: at least one second excitation source (132) configured to emit electromagnetic radiation (E S2 ) in the ultraviolet and / or visible field toward the second wall of the reservoir, the second wall (114, 432) being transparent to the electromagnetic radiation (E S1 , E S2 ) so that the volume of the inhomogeneous sample (S) that can be illuminated by the first excitation source (122) at least partially corresponds to the volume of the inhomogeneous sample that can be illuminated by the second excitation source (132); and second acquisition means (134) for acquiring a fluorescence spectrum (S f1 , S f2 ) of the inhomogeneous sample (S), The first infrared spectroscopy sub-assembly (120) comprises a diffusing and transparent optical element (140) for the electromagnetic radiation (E S1 ) emitted by the first excitation source (122), positioned between the first excitation source (122) and the first wall (112, 422) of the reservoir or between the second wall (114, 432) of the reservoir and the first collection device (124), outside the optical path of the electromagnetic radiation (E S2 ) emitted by the second excitation source (132) and outside the solid angle for collecting the fluorescent signal emitted by the non-homogeneous sample (S) when exposed to the electromagnetic radiation (E S2 ) emitted by the second excitation source (132). - a processing module (200) connected to the measurement module (100) by a communication network (300) and comprising a processor (220) configured to analyze data obtained by infrared spectroscopy and fluorescence spectroscopy.

2. The apparatus (1) as claimed in claim 1, characterized in that, - the transparent optical element (140) constitutes the first wall (112, 422) of the reservoir.

3. An apparatus (1) as claimed in claim 1 or 2, characterized in that - the first wall (112, 422) of the reservoir is movable along an axis (XI) perpendicular to the plane (PI) passing through the first wall (112, 422).

4. The apparatus (1) according to claim 1, characterized in that The second wall (114, 432) of the reservoir (110, 410) is anti-reflective to electromagnetic radiation (E S2 ) emitted by the second excitation source (132).

5. The apparatus (1) according to claim 1, characterized in that - the second excitation source (132) is located between the second wall (114, 432) and the first acquisition device (124).

6. The apparatus (1) as claimed in claim 1, characterized in that, - an axis (X') passing through the second acquisition device (134) and an intermediate plane and substantially perpendicular to the second wall (114) of the reservoir forms an angle a with respect to an axis passing through the first excitation source (122) and the second acquisition device (134).

7. The apparatus (1) as claimed in claim 1, characterized in that, The first excitation source (122) emits broadband polychromatic electromagnetic radiation (E S1 ), the first excitation source (122) comprising a high-power halogen incandescent source.

8. The apparatus (1) as claimed in claim 1, characterized in that, The second excitation source emits monochromatic electromagnetic radiation (E S2 ), the second excitation source (132) comprising one or more LEDs.

9. The apparatus (1) as claimed in claim 1, characterized in that, - an enclosure comprising a holding system (400) for holding the heterogeneous sample, the enclosure comprising an internal surface against which the holding system (400) is applied.

10. The device (1) as claimed in claim 9, characterized in that, - a holding system (400) for holding the heterogeneous sample, the system comprising: a) a reservoir (410) comprising a first enamel part (420) equipped with the first wall (422) and a second enamel part (430) equipped with the second wall (432), the first enamel part (420) being removably mounted on the second enamel part (430), b) a support block (450) for positioning the holding system (400), the support block comprising a connection portion (460) and a base (454) forming a bend with the connection portion (460) in the apparatus (1), c) a removable portion (470) comprising an enclosure (472) receiving the reservoir (410), the second enamel part (430) being fixed to the removable portion (470), the removable portion (470) being removably connected with respect to the connection portion (460), d) a hinged portion (480) comprising an opening (482), the hinged portion (480) pivoting on the support block (450) and being able to pass through a mounting position, wherein the hinged portion is distanced from the detachable portion (470) in a position of use, wherein the hinged portion is folded down on the detachable portion (470), the opening (482) being opposite the reservoir (410), the hinged portion (480) comprising compressible means (486a, 486b, 488a, 488b) which allow the holding system (400) to adhere to an internal surface of the casing of the measuring module (100) receiving the holding system (400) when the hinged portion is in the position of use.

11. A method for analyzing a non-homogeneous sample (S) with the device (1) according to any one of the preceding claims, comprising the steps of: A) acquiring a transmission spectrum (S i ) of the heterogeneous sample (S) with the first infrared spectroscopy sub-assembly (120) B) acquiring a fluorescence spectrum (Sf) of the heterogeneous sample (S) with said second fluorescence spectroscopy sub-assembly (130) f1 , S f2 ) C) analyzing the data obtained by infrared spectroscopy and fluorescence spectroscopy by means of the processing module (200), the processor (220) being configured to determine from the data from the analysis at least one criterion characterizing the non-homogeneous sample, D) coupling the data obtained by infrared spectroscopy and fluorescence spectroscopy at the level of the spectra by means of the processing module, by concatenation of the spectra previously processed and by correlation of the scores resulting from the decomposition of each spectrum, for constructing a linear or non-linear model and obtaining a calibration of a descriptive criterion of the state of the non-homogeneous sample.

12. The method of claim 11, wherein, The descriptive criterion is a technical, sensory or nutritional and sanitary quality criterion.

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