Apparatus for spectroscopic analysis of a sample and method for analyzing a sample using such apparatus

Abstract

We provide an apparatus for analyzing heterogeneous samples. [Solution] The apparatus comprises a reservoir 110 configured to contain a sample, and a measurement module 100 having a first infrared spectroscopy subassembly and a second fluorescence spectroscopy subassembly. The first subassembly includes a diffusive optical element 140 positioned to enable highly accurate and reliable infrared spectroscopy measurements without degrading fluorescence spectroscopy measurements performed on the same sample. The apparatus further comprises a processing module 200 connected to the measurement module 100 by a communication network and equipped with a processor configured to analyze data obtained by infrared spectroscopy and fluorescence spectroscopy.

Description

[Technical Field]

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

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

[0003] Within the scope of the present invention, a sample is more specifically a heterogeneous sample that may be solid (grains, crushed biscuits or potato chips, dough) or powder (wheat flour, powdered milk). A heterogeneous sample in the sense of the present invention is a sample that contains elements of various highly absorbent sizes. For example, a sample may contain impurities. However, in the case of a grain sample, the heterogeneity of the sample can also mean that it retains its particle size.

[0004] The present invention has applications in the agricultural industry, particularly in the cereal or dairy industry. The invention aims to enable the analysis of samples at different stages of their development by the experts concerned. In the agricultural industry, especially in cereal or dairy, industrial procedures require precise knowledge of the characteristics and quality indices of the analyzed sample (wheat, alveograph, Hagberg drop number in farinograph, or bread-making test for dough). As part of this, sample analysis utilizing spectroscopic techniques allows for the extraction of all physicochemical information readily conveyed in various functionalities of a product in tens of seconds, through the construction of calibrations between spectral information and criteria describing functionality. [Background technology]

[0005] Spectroscopic instruments employing different analytical methods are known, making it possible to obtain physicochemical information about samples. These analytical methods include conventional fluorescence spectroscopy and infrared spectroscopy.

[0006] Patent Document 1 discloses a commercially available measuring instrument that enables physicochemical analysis of a sample by infrared spectroscopy and fluorescence spectroscopy. The instrument comprises a single light source and a monochromator that allows the wavelength of the emitted beam to be changed over a spectral range suitable for performing two types of measurements. The instrument comprises a set of mirrors and reflectors that allow the beam emitted by the light source to take various optical paths, at least one of which is dedicated to infrared spectroscopy and at least one of which is dedicated to fluorescence spectroscopy.

[0007] If this instrument actually allows measurements to be taken on the same sample, the analyzable sample volume is 1 cm³. 3 Indeed, this type of instrument is primarily used in academic settings where the observed sample is often a very small, homogeneous model sample. However, if this volume is expressed as the number of grains, it represents only a small number of grains, and even then, they are very small in size. However, in the agricultural industry, particularly with grains or dairy products, the samples investigated (grains, dough, powder, etc.) are not only generally very heterogeneous in size, shape, and even composition, but also have much larger volumes, such as representing the contents of a silo (several thousand cubic meters). Furthermore, while this instrument allows for the analysis of less absorbent samples such as liquid samples, thin layers, paper layers, and precious metals, it is not suited to analyzing highly absorbent samples.

[0008] To accurately measure heterogeneous sample parameters as defined above, and in accordance with industrial standards, adapted equipment has been developed.

[0009] Patent Document 2 describes a spectroscopic analyzer that enables the measurement of such a sample using two types of measurements. The apparatus comprises a first module dedicated to infrared spectroscopic analysis. This module comprises a chamber with a light source that emits near-infrared and infrared electromagnetic radiation to illuminate the sample, a network monochromator detector or filter that reads the transmittance spectrum of the sample, and a placement intended to house the sample. The apparatus further comprises a second module specifically dedicated to fluorescence spectroscopic analysis. This module comprises a chamber with a light source that emits electromagnetic radiation intended to illuminate the sample, so that the sample emits a typical fluorescence signal under the influence of this radiation. The module also comprises a fluorescence detector capable of measuring the signal emitted by the sample, and a placement reserved for the sample.

[0010] Therefore, two operating modes are possible, each associated with a specific configuration. In the first configuration, the material sample is pre-separated into two samples, each moved toward a specific module, particularly for the purpose of performing certain measurements; in the second configuration, the material sample is moved sequentially from one module to the other.

[0011] When separating a sample into two samples, additional operations are required to separate the samples. Furthermore, the sample volume (region) analyzed by infrared spectroscopy is never the same as the sample volume (region) analyzed by fluorescence spectroscopy, because the two samples are always distinct, and similarly, they all originate from the same starting sample, and this heterogeneity of the starting sample is precisely the reality.

[0012] When moving a sample continuously between two modules of an instrument, additional operations are required to move the sample from one module to another. Furthermore, with this configuration, it is always impossible to guarantee that the volume (area) of the sample analyzed by infrared spectroscopy is the same volume (area) as the independent test sample analyzed by fluorescence spectroscopy, covering the same physicochemical reality due to dispersion. In fact, if the solid sample is of heterogeneous nature, there is always a suspicion that the subsample being analyzed does not represent the initial sample, and even if the sample does represent the initial sample, the positioning of the sample within the measurement chamber is not the same during the movement of the sample between the two modules. This inevitably affects the measurement.

[0013] Therefore, the above-mentioned spectroscopic analyzers have several drawbacks, as they are unable to analyze various highly absorbent, heterogeneous samples of different sizes, or they are unable to perform infrared and fluorescence spectroscopy measurements on the same sample without having to move the sample or separate it into two.

[0014] This result indicates that conventional devices do not allow for the optimized combination of data obtained by infrared spectroscopy and fluorescence spectroscopy because the image of the sample measured by infrared spectroscopy does not match the image of the same sample measured by fluorescence spectroscopy. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] International Open Publication WO2019 / 118800 (A1) Brochure [Patent Document 2] European Patent Application Publication EP1850117 (A1) [Overview of the Initiative]

[0016] The present invention makes it possible to overcome the above-mentioned drawbacks, and for this purpose, proposes an apparatus for analyzing heterogeneous samples, said apparatus, - Measurement module and, - It is characterized by comprising a processing module. The measurement module then comprises the following: ○ A reservoir configured to accommodate the aforementioned sample, comprising a first wall and a second wall opposite (facing) the first wall, ○ A first infrared spectroscopy subassembly comprising a first excitation source configured to emit electromagnetic radiation in the infrared field and / or near-infrared field to a first wall of a reservoir, the first wall being transparent to infrared electromagnetic radiation, and a first means for acquiring a transmittance spectrum, ○ A second fluorescence spectroscopy subassembly comprising: at least one second excitation source configured to emit ultraviolet and / or visible field electromagnetic radiation into a second wall of a reservoir, the second wall being transparent to electromagnetic radiation, such that the volume (region) of the sample that can be illuminated by the first excitation source at least partially coincides with the volume (region) of the sample that can be illuminated by the second excitation source; and a second means for obtaining the fluorescence spectrum of the sample; Equipped with, ○ The first subassembly comprises a diffusive and transparent optical element for electromagnetic radiation emitted by the first excitation source, the optical element positioned outside the optical path of electromagnetic radiation emitted by the second excitation source and outside the solid angle to collect a fluorescence signal emitted by a sample when the sample is exposed to electromagnetic radiation emitted by the second excitation source, between the first excitation source and the first wall of the reservoir, or between the second wall of the reservoir and the first acquisition means. Furthermore, the processing module 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.

[0017] Therefore, the apparatus is designed to enable the analysis of various highly absorbent, heterogeneous solid or powder samples such as grains, flour, and dough. Furthermore, the apparatus allows for the performance of infrared and fluorescence spectroscopy measurements within a single module, without the need to move the sample to be analyzed from one module to another or to separate it into two for two different measurements. In such a configuration, the volume (or region) of the sample analyzed by infrared spectroscopy always coincides, at least partially, with the volume (or region) of the sample analyzed by fluorescence spectroscopy, thereby enabling the correlation of data from the two measurements. Moreover, the number of operations is reduced, thereby reducing the temporal effects of the measurements and the time spent performing them. This makes the apparatus according to the present invention particularly suitable for physicochemical analysis in industrial environments.

[0018] The problem associated with measuring the transmittance of highly absorbent samples is solved by using diffusive and transparent optical elements.

[0019] Conventionally, when performing infrared spectroscopy (transmittance and / or reflectance) on heterogeneous samples of various sizes with very high absorbency, there is a difference in transmitted light intensity between measurements with and without the sample, with an intensity ratio of approximately 20,000. To solve this problem, there are two natural solutions. The first method involves adding an absorbing element to the optical path between the light source and the detection means during the measurement without the sample. The absorbing element makes it possible to obtain an intensity comparable to that with and without the sample, but it alters the optical path between the two measurements. Therefore, an additional "component" must be considered in the resulting spectrum, and possibly the spectrum that is removed, which can prove to be complex. The second solution involves altering, i.e., attenuating, the spectrum of the light source itself by changing the light intensity between the two measurements. The problem thus raised is the problem of measurement reproducibility.

[0020] A diffusive and transparent optical element allows for the diffusion of radiation emitted by a light source during infrared spectroscopic measurements without a sample, thus reducing the intensity of light transmitted to the detector during the measurement. However, during measurements with a sample, it diffuses the radiation emitted by the light source, but the measurement is less than that of the heterogeneous sample itself due to the presence of elements of various sizes and highly absorbent elements. This is because it constitutes a neutral and passive element, but it hardly attenuates the radiation from the light source compared to the attenuation by the sample itself, without losing information. Therefore, it is possible to significantly reduce the intensity ratio between two measurements without extending the measurement time, extending the length of the optical path, adding any elements to the excitation source, and / or changing the optical spectrum of the excitation source. Thus, with respect to specific solutions of the prior art, the present invention makes it possible to improve the reproducibility of measurements, provide greater robustness, and avoid the need to change the light source between two measurements.

[0021] However, the integration of such diffusive optical elements within a single measurement chamber of the apparatus is not always obvious, as fluorescence measurements must also be performed on the same sample, which is inherently very sensitive to diffusion. To address this problem, the diffusive optical elements are positioned outside the optical path of electromagnetic radiation emitted by the second excitation source and outside the solid angle to collect the fluorescence signal emitted by the sample when the sample is exposed to electromagnetic radiation emitted by the second excitation source, either between the first excitation source and the first wall of the reservoir, or between the second wall of the reservoir and the first acquisition means. This positioning makes it possible to perform infrared spectroscopy on samples of various sizes and highly absorbent, heterogeneous samples without interfering with fluorescence spectroscopy. Thus, the claimed apparatus enables reliable and highly accurate infrared and fluorescence spectroscopy on the same sample.

[0022] The apparatus of the present invention makes it possible to improve the compatibility (agreement) between sample images measured by infrared spectroscopy and sample images measured by fluorescence spectroscopy, and thus enables the optimization of combining data obtained by infrared spectroscopy and fluorescence spectroscopy.

[0023] According to the different features of the present invention, which can be adopted together or separately, - The optical element constitutes the first wall of the reservoir, - The optical element is positioned between the first excitation source and the first wall of the reservoir on the optical path between the first excitation source and the first acquisition means. - The first wall of the reservoir is movable along an axis perpendicular to the plane passing through the first wall, - The second wall of the reservoir is anti-reflective (anti-reflective) against electromagnetic radiation emitted by the second excitation source. - The second excitation source is positioned between the second wall and the first acquisition means. - An axis passing through the second acquisition means and the central plane and substantially perpendicular to the second wall of the reservoir forms an angle α with respect to the axis passing through the first excitation source and the second acquisition means. - The first excitation source consists of a high-power halogen incandescent source. - The second excitation source emits monochromatic electromagnetic radiation, - The second excitation source consists of one (or more) LEDs. - The apparatus comprises a housing for receiving a sample holding system, the housing having an inner surface that the holding system contacts and flattens, - The device is equipped with a sample holding system, The sample holding system is - A reservoir comprising a first glass-fitted portion having a first wall and a second glass-fitted portion having a second wall, wherein the first glass-fitted portion is removably attached to the second glass-fitted portion, - A support block comprising a connecting portion and a base that positions the holding system and forms a bent portion together with the connecting portion within the device, - A removable part comprising a housing for receiving the reservoir, wherein the second glass-fitted portion is fixed to the removable part, and the removable part is detachably connected to a connecting portion, - A connecting portion having an opening, the connecting portion being pivotably mounted to a support portion and being able to move from a mounting position away from a removable portion to a use position where it is folded onto the removable portion and the opening is on the opposite side of the reservoir, the connecting portion comprising compressible means that allows the connecting portion to abut against (or be made to abut against) the inner surface of the housing of the module that receives the retaining system when the connecting portion is in the use position, the connecting portion It is equipped with.

[0024] The present invention further relates to a method for analyzing a sample using the apparatus described above, the method comprising the following steps, namely: A) A step of obtaining the transmittance spectrum of the sample using a first infrared spectroscopic subassembly, B) A step of acquiring the fluorescence spectrum of the sample using a second fluorescence spectroscopy assembly, C) A step of analyzing data obtained by infrared spectroscopy and fluorescence spectroscopy using a processing module, wherein the processor is configured to determine at least one criterion that characterizes the sample from the data arriving from the analysis. D) A step of constructing a linear regression or nonlinear model by combining data obtained by infrared spectroscopy and fluorescence spectroscopy at the spectral level using a processing module, by concatenating pre-processed spectra and by associating scores derived from the decomposition of each spectrum, in order to obtain calibration of descriptive criteria for the state of the sample, such as technical, sensory, nutritional, and hygienic quality standards. Includes.

[0025] Other objects and features of the present invention will become clearer in the following description with reference to the accompanying drawings. [Brief explanation of the drawing]

[0026] [Figure 1a] This is a schematic diagram of an analytical apparatus according to a first embodiment of the present invention, in which the optical element is positioned between the first excitation source and the first wall of the reservoir, and the optical element forms part of the reservoir. [Figure 1b] This is a schematic diagram of an analytical apparatus according to one embodiment of the present invention, in which the optical element is positioned between the first excitation source and the first wall of the reservoir, and the optical element is a separate element of the reservoir. [Figure 1c] This is a schematic diagram of an analytical apparatus according to one embodiment of the present invention, in which the optical element is arranged between the second wall of the reservoir and the first excitation source. [Figure 2a] Figure 1a is a side view of the analytical apparatus. [Figure 2b] Figure 1b is a side view of the analytical apparatus. [Figure 3] This is a perspective view of the support for the second excitation source. [Figure 4a] This is a perspective view of a system for holding powdered, viscous, or dough-like samples for an apparatus for analyzing samples according to the present invention. [Figure 4b] Figure 4 is a perspective view of the retaining system, showing one of the faces of the retaining system. [Figure 5] Figures 4a and 4b are enlarged exploded views of the reservoir of the holding system shown. [Figure 6a] This figure shows the components associated with fluorescence in the raw spectrum obtained during step B) by applying the method according to the present invention to a barley sample (solid line) and by fluorescence spectroscopy using a reference method known from the prior art (dotted line) for an excitation wavelength of 340 nm. [Figure 6b] This figure corresponds to the spectrum in Figure 6a after Gaussian filtering. [Figure 6c]This figure shows a series of spectra obtained during step B) by repeating the method according to the present invention on the same barley sample for an excitation wavelength of 340 nm. [Figure 6d] This figure shows a series of spectra obtained by fluorescence spectroscopy using a known reference method from conventional techniques for a single, identical barley sample at an excitation wavelength of 340 nm. [Figure 6e] This figure shows the residues from each of the spectra in Figure 6c relative to the average spectrum. [Figure 6f] This figure shows the residues from each of the spectra in Figure 6d relative to the average spectrum. [Figure 7a] This figure shows the components associated with fluorescence in the raw spectrum obtained during step B) by applying the method according to the present invention to a barley sample (solid line) and by fluorescence spectroscopy using a reference method known from the prior art (dotted line) for an excitation wavelength of 385 nm. [Figure 7b] This figure corresponds to the spectrum in Figure 7a after Gaussian filtering. [Figure 7c] This figure shows a series of spectra obtained during step B) by repeating the method according to the present invention on the same barley sample for an excitation wavelength of 385 nm. [Figure 7d] This figure shows a series of spectra obtained by fluorescence spectroscopy using a known reference method from conventional techniques for a single, identical barley sample at an excitation wavelength of 385 nm. [Figure 7e] This figure shows the residues from each of the spectra in Figure 7c relative to the average spectrum. [Figure 7f] This figure shows the residues from each of the spectra in Figure 7d relative to the average spectrum. [Figure 8a] This figure shows the PLS regression (RMSECV = 0.022%) obtained by relating the values ​​measured by infrared spectroscopy using a known reference method from the prior art (horizontal axis) to the predicted values ​​obtained by cross-validation (vertical axis) for each sample of a batch of 204 wheat flours. [Figure 8b] This figure shows the MLR regression (RMSECV = 0.018%) obtained by relating the values ​​measured by fluorescence spectroscopy using a known reference method from the prior art (horizontal axis) to the predicted values ​​obtained by cross-validation (vertical axis) for each sample of a batch of 204 wheat flours. [Figure 9] This figure shows a continuous PLS regression (RMSECV=0.008%) achieved by using together the ash value for wheat flour (horizontal axis), measured by infrared spectroscopy and fluorescence spectroscopy according to the method of the present invention, and the predicted value obtained by cross-validation for each sample of a batch of 204 wheat flours (vertical axis) in order to construct the calibration. [Modes for carrying out the invention]

[0027] Referring to Figure 1a, the present invention relates to an apparatus 1 for analyzing a sample S, comprising a measuring module 100 and a processing module 200 connected to the measuring module 100.

[0028] The measurement module 100 includes a reservoir 110 for housing the sample S, a first infrared spectroscopy subassembly 120, and a second fluorescence spectroscopy subassembly 130.

[0029] The first infrared spectroscopy subassembly 120 and the second fluorescence spectroscopy subassembly 130 differ in the elements that comprise them, but these elements are localized within a common module. Thus, in contrast to known systems, the first subassembly 120 and the second subassembly 130 do not form submodules that are spatially separated from each other, such as simply two boxes placed side by side, but rather form subassemblies in which their elements are optimally arranged within a single measurement module 100.

[0030] As will be shown in detail below, this optimal arrangement allows infrared spectroscopy and fluorescence spectroscopy measurements to be performed by the first subassembly 120 and the second subassembly 130, respectively, without the need to move or separate the sample, thereby reducing the number of operations, performing analysis on exactly the same sample, and improving the reproducibility of the measurements. Furthermore, the time frame for performing two measurements on the same sample is established to be no more than one minute, which allows manufacturers to estimate a quantitative standard of grain from which real-time certification is possible in a short time. As will be more optimally described below, the arrangement of the reservoir 110 and the elements of the first and second subassemblies 120 and 130 within the measurement module 100 according to the present invention is particularly ingenious because it allows infrared spectroscopy and fluorescence spectroscopy measurements to be performed in a short time on the same sample S using a single measurement module 100.

[0031] The reservoir 110 for containing the sample comprises a first wall 112 and a second wall 114 facing the first wall 112.

[0032] The reservoir 110 may have any shape, as long as it includes the first and second walls 112, 114 as defined above. For example, the reservoir 110 may be a parallelepiped. In this case, the first and second walls 112, 114 can be formed at the levels of two opposing faces of the parallelepiped. The reservoir 110 may also be cylindrical. In this case, the first and second walls 112, 114 correspond to the cylindrical base. These are non-limiting examples.

[0033] The reservoir 110 is advantageously partitioned into a volume intended to accommodate the sample S. The volume of the reservoir 110 is advantageously about 100 mL. Furthermore, each of the first and second walls 112, 114 is tens of centimeters wide. 2 Preferably about 20 cm 2This provides an illuminated surface. Importantly, the illuminated surface allows for measurements that represent the sample despite its non-uniformity, while ensuring a suitable measurement time (approximately 1 minute) and a suitable instrument size (limited bulk). Therefore, the use of several smaller sub-samples, which would not only fail to adequately represent the batch being analyzed but also require longer measurement and analysis times, is avoided. Thus, the dimensions of the reservoir are sufficient for manufacturers to examine in detail the material quantities that represent all of the product they wish to characterize from infrared and fluorescence spectroscopy measurements. The dimensions of reservoir 110 are also suitable for performing measurements using both types of spectroscopy without excessively increasing the length of the optical path between the excitation source and detector of the first and second sub-assemblies 120, 130. Beyond these considerations, reservoir 110 can have any dimensions that the instrument user deems suitable for the samples they wish to analyze.

[0034] Preferably, the reservoir 110 may also be provided with a movable wall that allows the volume of the reservoir to be adapted depending on the type of heterogeneous sample (granular, powdery, or dough-like). The movable wall can be any of the walls of the reservoir 110. Thus, it is possible to decrease / increase the depth of the reservoir that determines the optical path of the light beam, thereby allowing smaller / larger grains to be analyzed, which have light absorbance levels inversely proportional to their size. If this is the first wall 112 of the reservoir, the first wall 112 is therefore preferably movable along an axis X1 perpendicular to the plane P1 through the first wall 112. According to an example of one embodiment shown in Figure 1a, the first wall 112 extends along a substantially vertical plane P1. Thus, the axis on which the movable wall 112 moves is the horizontal axis.

[0035] According to a specific implementation of the apparatus according to the present invention shown in Figures 4a, 4b, and 5, the analytical apparatus 1 includes a sample holding system 400 configured to accommodate and input the same number of granular and powdered samples as the dough-like sample.

[0036] The holding system 400 includes a reservoir 410 for housing samples, which can be seen better in Figure 5. The reservoir 410 comprises a first glass-filled section 420 having a first wall 422. This further comprises a second glass-filled section 430 having a second wall 432. The term “glass-filled” does not limit the scope of the invention in any way and is specified to be glass, without including any material from which the transparent wall is made. In fact, this 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 glass-filled section 420 and is intended to house an empty volume for housing samples. The first glass-filled section 420 is removablely attached to the second glass-filled section 430, i.e., the first glass-filled section 420 can be removed from the second glass-filled section 430.

[0037] The holding system 400 further comprises a support block 450, a removable part 470, and a connecting part 480.

[0038] The support block 450 allows the holding system 400 to be positioned within the measuring module 100, and in particular, allows for adjustment of the height position of the reservoir 410. It comprises a connecting portion 460 and a base 454 that forms an angle / curve(part) together with the connecting portion 460, the base allowing for easy gripping by the user.

[0039] When the holding system 400 is inserted into the module 100, the gripping base 454 comes into contact with the module 100, allowing the connecting portion 460 and the removable portion 470 to extend within the module 100. Thus, the connecting portion 460 itself enables the removable portion to be properly positioned within the module 100 for measurement.

[0040] The holding system 400 can be positioned in the optical path within a housing provided in the measurement module 100 for this purpose, and thus the base 454 can function as a contact point. Alternatively, the holding system 400 can be positioned at the level (height) of the aperture 150 shown in Figures 2a and 2b, and can serve to distribute the sample S. Thus, the holding system 400 also functions as a shield to prevent ambient light from entering the measurement module 100. In this configuration, as shown in Figure 4b, the holding system 400 appears to be suspended upside down, and the base 454 and connectors are positioned within the aperture 150 to prevent any detachment from the holding system 400. If the holding system 400 is not positioned in this location, a cover can be used as a shield for the aperture 150 during measurement.

[0041] The removable portion 470 comprises a housing 472 that receives the reservoir 410. The removable portion 470 is preferably detachably connected to the connection portion 460. In Figure 4a, the removable portion 470 is shown in a removable position, and in Figure 4b, the removable portion is shown in a mounted position. The second glass-fitted portion 430 is fixed to the removable portion 470 by being immovable within the removable portion.

[0042] The connecting portion 480 includes an opening or orifice 482. The connecting portion is pivotably mounted to the support block 450. When it pivots relative to the support block 450, the connecting portion can move from a mounting position away from the removable portion 470 to a use position (Figure 4b) where it folds onto the removable portion 470. When the connecting portion 480 is in the use position, the opening 482 is on the opposite side of the reservoir 410, which is the electromagnetic beam, in this case electromagnetic beam E, that reaches this side of the reservoir 410. S1 This makes it possible to avoid obstructing its passage.

[0043] Furthermore, the connecting portion 480 includes compressible means 486a, 486b, 488a, and 488b that enable the holding system 400 to be made flat against the inner surface of the housing provided in the measuring module 100 for this purpose when the connecting portion 480 is in the use position. Thus, the holding system 400 is in permanent contact with the housing, and in particular with the inner surface of the housing. With this configuration, the holding system 400 of the apparatus 1 has the same mechanical and optical positioning from one use to the other without the user having to prove that they are authorized or perform rigorous visual inspections. Thus, it enables repeatable measurements with various samples. Therefore, this configuration is preferable to a configuration in which the holding system is positioned at the height of the opening 150.

[0044] In either case, the sample has a fixed position within the measurement module 100.

[0045] In this regard, the sample S whose properties are to be identified is a solid. As already mentioned, this is more specifically a sample of grains, powders, doughs, and generally, a sample of a product manufactured in the cereal or dairy industry. The sample may be of any size, the only limitation being the dimensions of the reservoir 110. That said, the size of the sample is preferably adapted so that the amount of sample extracted represents the aggregate from which the sample was extracted. The sample is heterogeneous in the size of its elements, as well as in its shape. This may contain impurities and, generally, some foreign matter that is not strictly the main element in the sample. Conventionally, the whole challenge of infrared and fluorescence spectroscopy measurements may lie in the fact that, in order to assess the quality of the analyzed sample S, one must identify the proportion of such foreign matter. The sample may also be pre-crushed, as in the case of potato chips or biscuits.

[0046] Returning to Figure 1a, the first infrared spectroscopy subassembly 120 consists of the first excitation source 122, the optical element 140, and the transmittance spectrum S of the sample S. iR, S i comprises a first means 124 for obtaining i . As described above, all of these elements are not grouped together in an arrangement different from the arrangement of the elements constituting the second fluorescence spectroscopy subassembly, but are arranged to be optimal with the second fluorescence spectroscopy subassembly.

[0047] The first excitation source 122 is configured to emit electromagnetic radiation E S1 in an infrared field. It can also emit in the near infrared. This preferably can emit polychromatic and broad-spectrum electromagnetic radiation E S1 within a wavelength range between 700 and 1100 nm.

[0048] The first excitation source 122 emits electromagnetic radiation E S1 in the form of a beam onto the first wall 112 of the reservoir. The electromagnetic beam E S1 passes through the first excitation source 122 and propagates along the optical axis X centered on the first excitation source 122. Since the first wall 112 is transparent (permeable) to the electromagnetic radiation E S1 , the electromagnetic radiation E S1 can pass through the first wall 112 and thus irradiate the interior of the reservoir 110 and the sample S as required. Preferably, the first excitation source 122 illuminates the wall 112 in a uniform and collimated manner. "Collimated" means the fact that the light from the first excitation source has substantially parallel radiation, that is, it is spread without dispersing at a distance.

[0049] As an example, an excitation source 122 suitable for the implementation of the present invention is a high-power broadband halogen incandescent light source. In addition to the ability to illuminate in an infrared field, this type of light source has high inertia, which limits and even eliminates the scintillation effect due to fluctuations in the input current. In a variant form of the broadband spectrum source, several polychromatic or monochromatic sources covering the desired wavelength range can also be used.

[0050] Infrared electromagnetic radiation ES1 The interaction between the sample and the ion is of elastic nature. It depends on the properties of the molecules of the sample S being analyzed, the forces, and the axes of chemical bonds. Infrared electromagnetic radiation E S1 This refers to the electromagnetic radiation E S1 Absorption occurs only when the scalar product of the emission factor and 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 being investigated.

[0051] However, in order to obtain quantitative information, infrared spectroscopy uses at least two measurements to measure the spectrum of a sample without the influence of other elements located in the optical path, including the light source and detector. This is also true for the method of analyzing a sample according to the present invention. Herein, a general explanation is given to better understand the role of the optical element 140. The first transmittance spectrum S is called the reference spectrum. iR The transmittance spectrum S was obtained without using a sample, followed by the transmission spectrum S i This is obtained using the sample. Reference spectrum S iR The spectrum S obtained using the sample is shown. i This is a measurement of the contribution of the local environment, and in order to extract the actual signal from the sample alone, the spectrum S obtained using the sample is used. i It needs to be compared with that.

[0052] However, reference spectrum S iR and the spectrum S of the sample i The intensity ratio between and is very high, typically around 20,000. In fact, under identical illumination conditions in terms of intensity, the reference spectrum S iR It has very high transmittance, but the spectrum S containing the sample iThe latter has a lower transmittance. Two natural solutions have been proposed to reduce this transmittance difference. The first method involves adding an absorbing element to the optical path between the light source and the detection means during a measurement without a sample. The absorbing element makes it possible to obtain an intensity comparable to that with and without a sample, but it alters the optical path between the two measurements. Therefore, an additional "component" must be considered in the resulting spectrum, and possibly the spectrum that is removed, which can prove to be complex. The second solution involves changing the spectrum of the light source itself by changing the light intensity between the two measurements. The problem thus raised is the problem of measurement reproducibility.

[0053] The optical element 140 of the analytical apparatus 1 of the present invention makes it possible to avoid such limitations. In fact, the optical element 140 reacts to infrared electromagnetic radiation E emitted by the excitation source 122. S1 It is diffusive and transparent to radiation E. S1 The transparency (transmittance) of the optical element 140 to the radiation E is S1 This makes it possible not to hinder the propagation of electromagnetic radiation E. S1 This allows the light to be deflected in various directions, and therefore, especially when no sample S is present in the reservoir 110, it is possible to reduce the intensity of the light signal reaching the first acquisition means 124. In this case, the diffusion phenomenon is Rayleigh diffusion. The transparent and diffusive properties of the optical element 140 are accompanied by a certain number of phenomena, which do not have the same range, regardless of whether the reservoir 110 contains a sample or not.

[0054] According to the first embodiment shown in Figures 1a and 2a, the optical element 140 is positioned between the first excitation source 122 and the first wall 112 of the reservoir on the optical path between the first excitation source 122 and the first acquisition means 124. In other words, the optical element 140 is located on opposite sides (opposing sides) of both the first excitation source 122 and the first wall 112 of the reservoir, but not necessarily near the first excitation source 122 and the first wall 112 of the reservoir. In this embodiment of the present invention, the optical element 140 more specifically constitutes the first wall 112 of the reservoir. In other words, the first wall 112 and the optical element 140 form only one of them. In other words, the optical element 140 is integrated with the reservoir 110. Therefore, the optical element 140 is not affected by electromagnetic radiation E S1 It is localized on the optical path and positioned to interact with it before reaching the first acquisition means 124.

[0055] If sample S is not present in reservoir 110, beam E S1 The beam E is made to pass through the optical element 140 / first wall 112 and then the second wall 114 of the reservoir in succession before reaching the first acquisition means 124. By passing through the optical element 140, it can propagate exclusively in multiple directions and reach the first acquisition means 124 with reduced intensity without losing information. In the presence of the sample S in the reservoir 110, the beam E S1 The beam is made to pass through the optical element 140 / first wall 112, then the sample S, and finally the second wall 114 in succession before reaching the second acquisition means 124. As a result, even if the beam is diffused by the optical element 140, this diffusion is due to the beam E S1The diffusion that naturally occurs with the sample as it passes through is negligible. The negligible diffusion characteristics induced by the optical element 140 during measurement with the sample depend on the sample S being analyzed. If a grain or powder sample S diffuses naturally and therefore more than the optical element 140, this is not necessarily true for all other types of samples. Therefore, the signal measured with sample S in the presence of the optical element 140 is not of lower quality than the signal that would have been measured in the absence of the optical element 140. In short, the optical element 140 illuminates the sample's reference spectrum S under the same conditions when the first excitation source 122 is illuminating it at the same time as acquiring the two spectra. iR and spectrum S i This makes it possible to obtain it. This allows for freedom in choosing the means of acquisition.

[0056] The optical element 140 does not necessarily have to be positioned parallel to the first wall 112, as shown in the figure. Preferably, in this case, the optical element 140 generates isotropic diffusion in all directions. Therefore, as long as it is positioned on the optical path, the infrared electromagnetic beam E S1 While exhibiting its first function of diffusing, the infrared electromagnetic beam E around the optical axis X S1 The optical element 140 can be tilted with respect to the optical axis X without obstructing the propagation of the light. The optical element 140 can be manufactured, for example, by frosting glass.

[0057] According to the second embodiment shown in Figures 1b and 2b, the optical element 140 can be separated from the first wall 112 of the reservoir. In this configuration, the optical element 140 is presented in the form of an element distinct from the first wall 112. This can, in some cases, be positioned away from the reservoir 110 and stabilized using a support, although this is not mandatory. It can also be bonded to the first wall 112 of the reservoir, rather than to the first wall 112 itself. Whatever configuration is considered, i.e., whether the optical element 140 constitutes the first wall 112 or is separated from it, what is important within the scope of the invention is that the optical element 140 is not exposed to the electromagnetic beam E before it reaches the first acquisition means 124. S1 This means that it is localized along the optical path.

[0058] The first subassembly 120 further includes an optical element 140, as well as an electromagnetic beam E S1 A collimation lens 126 may be provided for the excitation source 122 located in the optical path. Preferably, the collimation lens 126 is positioned between the excitation source 122 and the optical element 140, the latter being integrated with the reservoir 110 or separated from the reservoir. The collimation lens 126 allows the electromagnetic beam E arriving from the excitation source 122 to be uniformly illuminated inside the reservoir 110, particularly the sample S. S1 This allows for parallelization. The information obtained from the measurements is more qualitative and quantitative.

[0059] In the modified embodiments of the first and second embodiments of the present invention, the optical element 140 is an electromagnetic beam E S1 This allows for both diffusion and simultaneous collimation. In this case, the optical element 140 performs the role of a collimation lens by performing the first function of diffusing the radiation arriving from the first excitation source 122, so a collimation lens 126 is not necessary. Such an element can be manufactured, for example, by frosting a collimation lens.

[0060] Furthermore, as described above, the first subassembly 120 includes a first means 124 for acquiring a transmittance spectrum. In this regard, the first acquiring means 124 enables the detection of electromagnetic signals emitted in the visible, near-infrared, and infrared fields, particularly at wavelengths between 750 and 2500 nm. As can be seen in the above section, the use of the optical element 140 provides freedom in the selection of the acquiring means.

[0061] In a preferred embodiment of the present invention, a single charge-transfer detector or a charge-coupled device (CCD) sensor is used for this first acquisition means 124. It is also possible to use a complementary metal-oxide-semiconductor (CMOS) sensor-based detector based on a photodiode or any other detection means known to those skilled in the art. In practice, it is preferable to use a detector with a monochromator. The monochromator allows for the selection of a desired spectral field, i.e., to adapt the signal acquisition to the analysis under consideration. A monochromator that can be considered is, for example, one (or more) chromatic filters or a spectrometer.

[0062] The first acquisition means 124 is advantageously aligned with the excitation source 122, the diffusive transparent optical element 140, and the reservoir 110 along the optical axis X. In other words, all these elements are on the optical path. The first acquisition means 124 has a field angle centered on the optical axis X. In short, what is important in this case is that the first acquisition means 124 is positioned along the infrared beam E S1 Reference signal S in the sample emitted under irradiation. iR and signal S i It is positioned to detect [something].

[0063] From the perspective of the infrared spectroscopic subassembly 120, the above configuration, which enables infrared spectroscopic measurements, is ingenious in that it provides a diffusive, transparent optical element 140, and even more so in that it does not interfere with fluorescence spectroscopic measurements performed on the same sample S. This will be explained in more detail below.

[0064] The second fluorescence spectroscopy subassembly 130 includes a second excitation source 132 and the fluorescence signal S of the sample S. f1 S f2 It comprises a second means 134 for obtaining.

[0065] The second excitation source 132 emits electromagnetic radiation E in an ultraviolet field. S2 It is configured to emit a light. This can also be emitted in a visible light field. According to a preferred embodiment, it can emit monochromatic radiation having wavelengths between 250 and 550 nm. An example of a second excitation source 132 that can be used in the analytical apparatus 1 according to the present invention consists of at least one light-emitting diode (LED) emitting wavelengths of 280 nm, 340 nm, 385 nm, or 420 nm. The advantage of LED light sources is their ability to illuminate strongly and uniformly. Furthermore, they have a long service life.

[0066] Preferably, the number of excitation sources 132 can be adapted according to the size of the surface to be analyzed. Therefore, if several second excitation sources 132 are used, a support 136 can be provided, configured to house the excitation sources 132 and thus hold them on a single support, as shown in Figures 1a and 1b. In this regard, in an example of one embodiment shown in Figure 3, the support 136 comprises an assembly 1360 and a support (not shown) that allows for stabilizing the assembly 1360. The assembly 1360 comprises a plurality of housings 1362 arranged circularly (within a circle) around a central opening 1364 of the support, in which the second excitation sources 132 can be fixed. In fact, the housings 1362 have dimensions suitable for receiving the second excitation sources 132 and include means for fixing the excitation sources 132, for example, by screws and / or nuts. Preferably, the assembly 1360 is removable so that it can be removed from the support 136.

[0067] In one modified example, a broad spectral source is used as the second excitation source 132, and electromagnetic radiation E is emitted in the ultraviolet field.S2 It can also emit a monochromator in combination with such an excitation source. In this configuration, the broad spectral source is pleochroic, and an electromagnetic beam E with a narrower wavelength range or a broader spectrum can be used. S2 To select a wavelength from this range, it needs to be associated with a monochromator. This configuration is more complex than the previously mentioned configuration, namely an LED light source. An example of a broad-spectrum source that emits light in the ultraviolet field is a deuterium lamp that emits light in the ultraviolet field at wavelengths from 180 nm to 370 nm.

[0068] The second excitation source 132 emits an electromagnetic beam E to the second wall 114 of the reservoir opposite the reservoir 110. S2 The diffusive transparent optical element 140 emits light, and in this case, the light is localized according to the first and second embodiments (Figures 1a, 1b, 2a, and 2b). The second excitation source 132 can be eccentric with respect to the optical axis X. If several excitation sources 132 are used, each excitation source can be eccentric with respect to the optical axis X, as shown in Figures 1a-1c. The excitation source 132 is advantageously tilted toward the center of the second wall 114, thereby enabling uniform and appropriate illumination of the second wall 114 by the excitation source. It is important in this case that the second excitation source 132 is positioned so as not to interfere with the acquisition of infrared and fluorescence spectra.

[0069] The second excitation source 132 emits an electromagnetic beam E into the second wall 114. S2 The fact that it emits is neither illustrative nor a simple choice of configuration. As stated before the detailed description of the present invention, the object of the present invention is to provide an apparatus 1 that enables infrared spectroscopy and fluorescence spectroscopy to be performed on the same sample S in a short time without the need to perform measurements in separate submodules, and therefore without the need to separate the sample into two or to transport it from one module to another. This choice of configuration makes it possible to perform infrared spectroscopy and fluorescence spectroscopy on the same sample without the elements of the first subassembly 120 required for infrared spectroscopy that would interfere with fluorescence spectroscopy.

[0070] In fact, because the fluorescence intensity is very low relative to the light source intensity, fluorescence is highly sensitive to diffusion, and diffusion itself depends on the physicochemical properties of the sample. Diffusion, even at low intensity, interferes with the fluorescence signal. While this does not prevent the extraction of quantitative data from it, the component due to diffusion in the spectrum significantly complicates the extraction of data useful for analysis and / or requires the use of filters, although filters currently have very limited effect on reducing the proportion of light due to diffusion in the final spectrum.

[0071] Due to its positioning between the first excitation source 122 and the first wall 112 of the reservoir, the diffusive optical element 140 can perform its role for infrared spectroscopy without interfering with fluorescence spectroscopy. In fact, fluorescence spectroscopy requires only illumination of the reservoir 110 if the sample S is required on the side of the second wall 114, i.e., opposite to the diffusive optical element 140. Thus, the electromagnetic beam E emitted by the second excitation source 132 S2 No interaction can occur between the optical element 140 and the first excitation source 122 and the second excitation source 132 of the reservoir 110, and the optimized illumination direction of the sample S, enable two types of measurements to be performed without one "interfering" with the other. Thus, the objective of the present invention is achieved, which is to enable infrared spectroscopy and fluorescence spectroscopy on the same sample within a shortened time frame. This configuration also enables the second subassembly 130 required for fluorescence spectroscopy to not interfere with infrared spectroscopy.

[0072] In the first and second embodiments of the present invention, when the diffusive optical element 140 is positioned between the first excitation source 122 and the first wall 112 of the reservoir, it should be noted that, while remaining within the inventive concept of the present invention, alternative positioning may be considered by those skilled in the art, as long as the optical element 140 is positioned so as not to interfere with fluorescence spectroscopy measurements and is positioned between the first excitation source 122 and the first acquisition means 124. The optical element 140 is positioned to receive the electromagnetic beam E emitted by the second acquisition means 134. S2 The optical element 140 is positioned so as not to interfere with the fluorescence spectroscopic measurement, and as long as it does not interfere with the fluorescence signal emitted by the sample when the sample is exposed to such a beam. By taking the above constraints into consideration, the optical element 140 does not prevent its detection by the first acquisition means 124 during the measurement, whether or not a sample is present, and does not interfere with the fluorescence signal emitted by the first excitation source 122. S1 As long as it is positioned to diffuse, it is positioned between the first excitation source 122 and the first acquisition means 124.

[0073] Therefore, in another embodiment of the present invention, the optical element 140 also receives electromagnetic radiation E emitted by the second excitation source 132 between the second wall of the reservoir 114 and the first acquisition means 124. S2 Outside the optical path, and electromagnetic radiation E emitted by the second excitation source 132 S2 It is also possible to position the optical element outside the solid angle for collecting the fluorescence signal emitted by the sample S when the sample is exposed to the light. In this embodiment, the second wall 114 of the reservoir cannot be made of optical elements 140 because it would inevitably interfere with fluorescence spectroscopy measurements. An example of a device 100 corresponding to such an implementation is shown in Figure 1c.

[0074] Furthermore, the second wall 114 of the reservoir is exposed to electromagnetic radiation E emitted by the second excitation source 132. S2 It is transparent (transparent) to the radiation E, and therefore, the radiation E S2It is possible for the radiation to pass through the second wall 114 and thus irradiate the inside of the reservoir 110 and the sample S. Furthermore, the second wall 114 of the reservoir is blocked by electromagnetic radiation E S2 It is anti-reflective (anti-reflective) to the second wall 114. The anti-reflective properties of the second wall 114 allow for an increase in the proportion of light that passes through the second wall 114 and reaches the sample S. Therefore, this allows for improved detection of the fluorescence signal, which can be proven to be relatively low, and thus allows for optimization of fluorescence spectroscopy.

[0075] Furthermore, the second wall 114 of the reservoir also emits infrared electromagnetic radiation E from the first excitation source 122. S1 It is transparent (transmissive) to infrared electromagnetic radiation re-emitted by sample S or its adjacent environment.

[0076] In this regard, as mentioned above, the support 136 also includes a central aperture 1364. The aperture 1364 is central in that it leaves a large, material-free open area around the optical axis X, which allows electromagnetic radiation generated by infrared and fluorescence spectroscopy measurements to pass through. The aperture 1364 is sized to allow as much beam as possible to pass through, which allows for the collection of the maximum amount of signal for infrared spectroscopic measurements. In one embodiment shown, the central aperture 1364 is circular, but this is not mandatory. The central aperture 1364 can be any other shape as long as it does not interfere with the collection of infrared signals.

[0077] The second acquisition means 134 is dedicated to fluorescence spectroscopy. In this regard, the second acquisition means 134 enables the detection of electromagnetic signals emitted in the ultraviolet and visible fields, more specifically at wavelengths between 200 and 550 nm. The second acquisition means 134 can be a CCD sensor, a CMOS sensor, a photodiode, or any other detection means known to those skilled in the art. For example, it is preferable to use the detector with one (or more) chromatic filters, or a monochromator such as a spectrometer.

[0078] The second acquisition means 134 is advantageously positioned at an angle α with the optical axis X. In other words, the axis X' passing through the central plane substantially perpendicular to the second acquisition means 134 and the second wall 114 of the reservoir is positioned at an angle α with the optical axis X. Thus, axis X' is the axis with respect to the optical axis X in which the second acquisition means 134 is located. Consequently, the second means 134 is not optically aligned with the other elements of module 100, namely the first excitation source 122, the optical element 140, the reservoir 110, the second excitation source 132, and the first acquisition means 124. From this, the second excitation source 132 is exposed to electromagnetic radiation E on both sides of the optical axis X. S2 It emits electromagnetic radiation, and only the portion of this electromagnetic radiation localized within the field of view of the second acquisition means 134 around the direction of axis X' is detectable.

[0079] Illumination of the second wall 114 by the second excitation source 132 generates specular reflection, which remains quite large despite the anti-reflective treatment of the second wall 114 of the reservoir. When incident radiation is reflected in a given direction like a beam reflected by a mirror, the reflection is called specular reflection(s). A considerable proportion of electromagnetic radiation is still reflected specularly in the direction of the optical axis X, which can cause saturation of the detection means. In this case, the second excitation source 132 is electromagnetic radiation E S2The light is emitted against the second wall 114, which passes through the optical axis X, inevitably generating specular reflection. The angle α that the second acquisition means 134 makes with the optical axis X is selected so that the second acquisition means 134 is not directly positioned on the optical path of the beam specularly reflected by the second wall 114 of the reservoir, which makes it possible to avoid saturation of the second acquisition means 134 while maintaining the maximum amount of fluorescence emitted isotropically by the sample. For example, the angle α takes a value equal to 10°.

[0080] The measurement module 100 described above can be grouped into a single module, and these elements can perform both infrared spectroscopic and fluorescence spectroscopic measurements without the need to separate the sample into two parts, thus eliminating the need to perform two separate analyses spatially and even temporally, or to perform two types of measurements consecutively over time. If the apparatus 1 according to the present invention allows two types of spectroscopic measurements to be performed on the same sample S within a time frame of several minutes, it is configured to also process the data resulting therefrom.

[0081] In this regard, the apparatus 1 according to the present invention also includes a processing module 200 connected to the measurement module 100, in addition to the measurement module 100. The processing module 200 may be a computer in a terminal, a smartphone, or any similar device having any type of electronic or computerized processing means, such as a control screen, a USB stick, a mobile memory card, or any other similar technology. Preferably, the processing module 200 is an embedded PC.

[0082] The processing module 200 is connected to a single measurement module 100 of the analyzer 1 via a communication network 300. The communication network 300 enables the processing module 200 to connect to the measurement module 100. The communication network 300 is a local network such as a wired network, Bluetooth network, Wi-Fi network, or Ethernet network. In any case, the communication network 300 is configured to transmit information between the processing module 200 and the measurement module 100 of the analyzer 1. Since the measurement module 100 is unique (one), there is therefore no interface between measurement and processing.

[0083] The processing module 200 includes a processor 220 and memory 240.

[0084] Memory 240 is configured to receive and store data transmitted by the communication network 300. This data is transmitted by infrared E emitted by the sample. S1 Emission and fluorescence E S2 The measurement module 100 may include any type of information measured by the measurement module, such as the wavelength of the radiation, the intensity measured from these radiations, or the corresponding electromagnetic spectrum.

[0085] The processor 220 is configured to analyze and / or process data obtained by infrared spectroscopy and fluorescence spectroscopy. In this regard, software for processing this data can be installed on the processor to automate the processing of this data in real time. Important within the scope of the present invention is that the processor 220 can process the data coming in from infrared spectroscopy and fluorescence spectroscopy continuously within a time frame of several minutes to extract evaluation factors and / or evaluation criteria from the investigated sample S. The operations performed by the processor 220 are described in more detail below with respect to the method for analyzing the sample S.

[0086] In fact, the present invention further relates to a method for analyzing a sample S, which is carried out by the analytical apparatus 1 described above. The method according to the present invention includes the following steps.

[0087] During the first step A), the transmittance spectrum S i However, this is obtained from the sample S using the first infrared spectroscopic subassembly 120. Theoretically, if it is possible to perform such a measurement directly, a reference infrared spectrum S, also called a sample-free spectrum, can be obtained. iR Without additional measurements, it is impossible to accurately quantify a phenomenon specific to the sample, namely the transmittance of the sample. As described above, the reference spectrum S iR This measurement allows for the quantification of the contribution of the local environment to the measurement of the transmittance spectrum of a sample.

[0088] Step A) of the method according to the present invention is advantageously substep Aa), Ab), Ac), Ad), and Ae), reference spectrum S iR Steps Aa) and Ab) relating to the measurement of the sample spectrum S are included, and therefore steps Ac) to Ae) are performed. i This relates to the measurement of [the substance], and is therefore performed together with the sample to be analyzed.

[0089] During substep Aa), the reservoir 110 receives electromagnetic radiation E generated by the first excitation source 122. S1 It is illuminated using electromagnetic beam E. S1 Before reaching the first acquisition means 124, the electromagnetic beam E passes through the optical element 140, then the first wall 112, the reservoir, and the second wall 114 of the reservoir in this order. S1 It traces a path along the optical axis X. The inside of the reservoir is empty and does not contain any samples. Furthermore, reservoir 110 remains filled with air and other elements present in the air, which are electromagnetic radiation E S1 It may absorb and reflect some of the light.

[0090] If the first wall 112 of the reservoir is formed by the optical element 140, then beam E S1 It is specified that the beam passes through the optical element 140, the inside of the reservoir, and the second wall 114 of the reservoir in sequence before reaching the first acquisition means 124. It is also specified that if the collimation lens 126 is optionally interposed between the first excitation source 122 and the optical element 140, the order in which the beam passes through the different elements is affected together. Furthermore, in embodiments in which the second excitation source 132 includes multiple excitation sources supported by a support 136, the electromagnetic beam E S1 It is specified that the light must pass through the aperture 1364 of the support positioned in the optical path.

[0091] During substep Ab), the reference transmittance spectrum S iR This is measured.

[0092] During substep Ac), reservoir 110 is filled with the sample S to be investigated. If comparative measurements must be performed between several samples, reservoir 110 is systematically filled with equal amounts of each sample.

[0093] Steps Aa) and Ab) are repeated between substeps Ad) and Ae), but this time the difference is that the sample S to be investigated is placed inside the reservoir 110. At the end of this second acquisition sequence, the transmittance spectrum S of the sample is obtained. i This is obtained.

[0094] Next, the data collected during step A), in particular the reference transmittance spectrum S of the sample, iR and S i These are analyzed and / or processed by the processor 220. Preferably, they are stored in the memory 240 of the processing module. This is returned to the following:

[0095] During step B of the method according to the present invention, the fluorescence spectrum S of the sample S is observed. f1 S f2This is obtained by the second fluorescence spectroscopy subassembly 130. The sample S associated with this is the exact same sample analyzed during step A). ​​In other words, this is not a sample that has been split to perform two different measurements. Furthermore, it should be noted that step B) is not necessarily performed after step A). ​​It can be performed equally before or after step A).

[0096] Step B) of this method includes the substeps Ba), Bb), Bc), and Bd) described below. At a constant integration time, if fluorescence spectroscopy measurements are performed over an expanded wavelength range, for example, 250 nm to 650 nm, the signal intensity may be available over part of this wavelength range but not over other parts, saturating the acquisition means. This stems from the dynamic range between diffusion and fluorescence. Indeed, fluorescence spectra always include a wavelength range in which diffusion is measured and a wavelength range in which the fluorescence signal itself is measured. However, the maximum intensity of the signal measured due to diffusion is greater than that due to the fluorescence phenomenon. The intensity ratio measured between the two measurements can be approximately equal to 100. However, these two components of the signal have equal importance for the purpose of physicochemical analysis of the sample. Therefore, it is desirable to return them to equivalent (or comparable) intensity levels.

[0097] During the first substep Ba), the reservoir 110 and sample S are subjected to electromagnetic radiation E emitted by the second excitation source 132. S2 It is illuminated by the electromagnetic beam E emitted by the second excitation source 132. Considering the arrangement of the elements of the second subassembly 130, S2 The electromagnetic beam E passes through the second wall 114 of the reservoir, and then through the sample in the same order. S2 The interaction between the sample S and the sample S generates a fluorescence signal specific to that sample S.

[0098] During the second substep Bb), the first fluorescence spectrum S of the sample S is obtained. f1is acquired simultaneously with step Ba) using the second acquisition means 134 at a predetermined integration time t1. The identification of this integration time may require a prior measurement by the sample S to be investigated in order to optimize either the proportion of the signal due to diffusion or the proportion of the signal due to fluorescence. The signal is considered to be optimized when the signal / noise ratio is high enough to enable the extraction of the desired parameters. Whatever it is, and as described in the above section, the signal measured by the second acquisition means 134 can prove that it is unusable over a part of this wavelength range considering the contributions of these two phenomena in the final spectrum, namely diffusion and fluorescence.

[0099] Between the third sub-step Bc) and the fourth sub-step Bd), the sub-steps Ba) and Bb) are repeated, but this time, the optimized integration time t2 is selected to measure either the other component of the signal, namely the proportion of the signal due to diffusion, or the proportion of the signal due to fluorescence for which the integration time was not optimized during sub-step Bb). From these steps, the second fluorescence spectrum S f2 is obtained.

[0100] For example, it may be considered to measure the fluorescence signal over the wavelength range of λ1~λ n . At the integration time t1, the fluorescence signal was unusable over the range λ1~λ m , but was available over the remaining range, i.e., λ m+i ~λ n , where i is the step between measurements. During the acquisition sequence of S f2 , if the pattern in which the fluorescence signal was unusable over the range λ1~λ m has a low signal / noise ratio, an integration time t2 greater than t1 is selected. Conversely, if the pattern in which the fluorescence signal was unusable over the range λ1~λ m is the saturation of the second acquisition means 134, an integration time t2 smaller than t1 is selected.

[0101] Thus, at the end of the second step B) of the method according to the invention, two fluorescence spectra S f1 and S f2 are obtained, which are collected and then processed by the processor 220. It should also be noted that the reference infrared spectrum S iR and the infrared spectrum S i associated with the infrared spectroscopy of the sample are also collected and processed by the processor 220.

[0102] In the embodiment described above, the fluorescence spectroscopy step B) was performed after the infrared spectroscopy step A). However, since both steps are independent, it is also possible to perform step B) before step A) without preconception.

[0103] During the third step C) of the method according to the invention, the data obtained by infrared spectroscopy and fluorescence spectroscopy are analyzed by the processing module 200, and the processor 220 is configured to determine at least one indicator characterizing the sample from the data resulting from the analysis. Step C) of the method according to the invention is a step implemented by a computer. The word "computer" has a broad meaning and means any means equipped with a processor and capable of executing tasks according to programmed commands. Whatever it is, from step C), at least one indicator characterizing the sample S to be investigated is obtained. In this regard, it can be clearly stated without doubt that this step is preferably carried out after steps A) and B).

[0104] Hereinafter, the processing of the infrared spectrum and the fluorescence spectrum obtained from steps A) and B) respectively will be described.

[0105] During the first sub-step Ca), from the reference spectra S iR and S i of the sample, the final transmittance spectrum S ifThis is determined. In this regard, median smoothing is first applied to more or less (±1) pixels to obtain the reference infrared spectrum S of the sample. iR and S i Defective pixels within can be removed. Secondly, this is the spectrum S of the sample. i The goal is to eliminate the contribution of the local environment to the sample signal S. i and reference signal S iR The ratio is calculated. At this stage, it should be noted that the intensity ratio between the two spectra is usually 1000. Therefore, by using a diffusive optical element, sample S iR Measurement without using and sample S i This makes it possible to divide the intensity ratio with the measurement using 20. This allows for the final transmittance spectrum S if This is obtained. The spectrum obtained in this way can also be standardized and converted back to a percentage value.

[0106] During the second substep Cb), the final fluorescence spectrum of sample S is obtained (considering the example above) spectrum S f1 and S f2 It is then expanded from. Hereafter, this spectrum will be referred to as the "final spectrum" S ff This is called [a specific term]. The concatenation of spectra is: 1) Spectra S measured for this purpose f1 or S f2 1) Reconstructing an optimized spectrum from the diffusion signal, 2) Other spectra measured for this purpose S f1 or S f2 To reconstruct an optimized spectrum from the fluorescence signal, and 3) to obtain a final spectrum S with a good signal / noise ratio for the diffusion spectral component as well as the fluorescence spectral component. ffTo obtain this, the optimized diffusion spectrum and fluorescence spectrum are grouped together. Thus, the signal / noise ratio of the diffusion spectrum to the fluorescence spectrum is returned to 100 over the entire spectrum, particularly over the portion of the spectrum corresponding to the fluorescence component, which is greater than the ratio of 10 in the unprocessed spectrum. f1 and S f2 The wavelength range over which it extends is specified as follows:

[0107] Continuing with the previous example, λ m+i from λ n Spectrum S, which corresponds to optimal fluorescence measurements performed over the wavelength range. f1 Therefore, from λ1 to λ m Spectrum S, which corresponds to optimal diffusion measurements performed over the wavelength range. f2 This can be linked together, where i is a natural integer corresponding to the step. The final fluorescence spectrum S obtained in this way. ff is from λ1 to λ n The spectrum is spread out and has good quality in the parts of the spectrum associated with the signal proportion derived from diffusion, as well as those associated with the signal proportion derived from fluorescence. Coupling can also make it possible to couple spectra that could only be measured with different excitation sources 132, for example, due to the cutoff wavelength defined by the LED. The final substep is to obtain the final spectrum S thus obtained. ff This consists of performing Gaussian smoothing.

[0108] In reality, spectrum S f1 and S f2 One of these corresponds to the "diffusive" component of the fluorescence spectrum, extending substantially over the wavelength range between 250 nm and the coupling wavelength, and the spectrum S f1 and S f2 The other of these corresponds to the "fluorescent" component of the fluorescence spectrum and extends substantially over a coupled wavelength range of 650 nm, and even beyond 650 nm. The coupled wavelength is the excitation wavelength (i.e., electromagnetic radiation E).S2 It lies beyond the wavelength and is at its minimum value within the wavelength range close to the excitation wavelength. In the case of measuring grains of cereals, the coupling wavelength is equal to the excitation wavelength applied between 10 and 20 nm.

[0109] Thanks to this combined measurement system, acquiring infrared and fluorescence emission transmittance spectra on the same subsample allows for the grouping of all spectral information provided by these two optical techniques—partially complementary information—to enhance knowledge of the heterogeneous sample being analyzed. Because the implemented instrument ensures that the spectra correspond to the same sample, the coherence between the information acquired by the two infrared and fluorescence techniques ideally allows, and only for the first time, to collect them in order to perform a merge of the information contained in each spectrum.

[0110] It should be emphasized that the conventional method (referred to as the reference method) does not have the third and fourth substeps Bc) and Bd). Fluorescence spectrum S f1 Only is obtained with intrinsic operating parameters. As a result, 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 the reference method, spectrum S f2 Since it is not obtained, the final fluorescence spectrum S f is spectrum S f1 It corresponds to.

[0111] Furthermore, in addition to the method of concatenating the spectra described above, other methods can be employed to utilize the information from these fluorescence and infrared spectra, and several such methods are possible.

[0112] However, before anything else, the infrared transmittance spectrum and the fluorescence emission transmittance spectrum must first be processed and then merged. This is preprocessing.

[0113] The fluorescence spectrum is processed to separate the diffusion of the fluorescence spectrum, thereby obtaining a pure fluorescence spectrum. Several methods can be considered to do this. • Truncation of the diffusion spectrum when this (diffusion) does not overlap with the fluorescence spectrum. • Modeling of diffusion patterns and removal of modeled diffusion • Use of chemometric tools such as ICA (Independent Component Analysis) that allow for the distinction between diffusion signals and pure fluorescence signals. And so on.

[0114] Therefore, for each measurement, the same number of fluorescence emission spectra and infrared transmittance spectra as the excitation (LED) wavelength are obtained.

[0115] There are two main methods for combining signals. They differ in their approach (or order of approach): one combines information, and the other reduces this information from thousands of variables to one or a few dozen, without losing any useful information. Different calibration or classification models can then be applied to these fewer new variables.

[0116] Therefore, the two main methods are as follows: This is a low-level method that combines reduced information or scores resulting from the decomposition of each spectrum. The following shows possible variable reduction methods. Thus, a limited number of variables are obtained, which contain almost all the initial information. These variables can then be modeled by different calibration or classification algorithms. This is a high-level technique that involves combining the spectra themselves before proceeding with the variable reduction step. The best way to combine spectral information is to concatenate the spectra. In this case as well, various variable reduction techniques, such as principal component analysis, can be applied. Therefore, the reduced information obtained by combining the two techniques is incorporated into a calibration model such as multiple linear regression or classification.

[0117] Here, we will consider (explor) various techniques applicable to each of these actions.

[0118] "Coupling": The spectrum is organized end-to-end, preferably by combining each fluorescence emission spectrum with increasing excitation wavelengths, followed by the infrared transmittance spectrum. In this case, several precautions are taken. • Spectra must be standardized so that each spectrum has the same weight within the assembly, and therefore they must be given similar intensity. For example, standardization can be done by area, by standardization by the standard deviation of the spectrum followed by centering, or by standardization by the maximum value, so that the intensity varies between 0 and 1. Next, it must be ensured that there is no break between the signal at the last wavelength of spectrum N-1 and the signal at the first wavelength of the next spectrum N. Various techniques are possible to achieve this, such as forcing the value to 0 if the part of the spectrum in question contains no information. Despite all of this, the spectrum must be smoothed to obtain a regular signal.

[0119] This is the method described above.

[0120] "Information Reduction": This reduction of information from spectral variables is also called spectral decomposition. Each intensity at each measured wavelength corresponds to a variable, and in this case, there is very high redundancy among all of these variables (highly correlated variables). Therefore, the idea is to extract independent information, the sum of which covers all of the initial information contained in the spectrum.

[0121] The most well-known decomposition method is principal component analysis, which ensures that each new variable, called a principal component, constitutes a vector orthogonal to the system composed of the other principal components. The number of components is determined by the capacity of the model to explain all spectral variances. However, from a certain level of decomposition, this variance now contains only noise.

[0122] For multi-pass structures such as 3D fluorescence structures, multi-pass techniques such as PARAFEC (PARAllel Factor analysis) can be applied. This involves identifying whether a single 3D structure or factor, or a single phosphor grouped together, contains all of the acquired fluorescence.

[0123] "calibration" Whatever spectral decomposition technique is used, a single or concatenated new variable is obtained (called a single factor or principal component), generally a limited number of about 10 to 20. Thus, each sample is represented by a linear combination of these variables and a specific weight for each of them. These weights generally have names for scores.

[0124] Echi=a i1 ×V1+a i2 ×V2+…a in ×V n + constant In the formula, a in Each variable V n These are the weights, and n is the number of variables obtained during decomposition.

[0125] Therefore, the score characterizes sample i with respect to this decomposition.

[0126] Therefore, during calibration, only these scores to which the target response is associated are used, and it is required that these be predicted by spectral measurements.

[0127] The most common calibration methods are PCR (principal component regression) or MLR (multiple linear regression) for linear mode calibration.

[0128] Another linear regression method, PLS (Partial Least Squares), has the special characteristic and advantage of reducing the connected spectrum of new variables while considering their correlation with the calibrated and predicted response. Thus, reduction and calibration are performed in a single step.

[0129] Furthermore, nonlinear methods can also be used as random forests, proximity techniques, or neuronal networks.

[0130] "An example of one embodiment of the analytical apparatus 1 according to the present invention" Whatever the example considered below, the processing module 200 is a computer, but can be any device equipped with a processor 220 as defined in the section above. With respect to the communication network 300, it is wired; however, it may be of any other nature.

[0131] The individual elements of the measurement module 100, which have been described in detail below, are interesting.

[0132] In one embodiment of the analytical apparatus 1, the optical element 140 consists of a glass wall with a diffuser, which is sold by Edmund Optics under reference number 84479 and also sold by Edmund Optics under reference number 83420. The diffuser consists of high-quality frosted glass having sufficient roughness to produce diffusion. The glass can be frosted by using a sanding method that allows for uniform diffusion across the entire surface.

[0133] In one embodiment of the analyzer 1, the first excitation source 122 consists of a high-power, broadband halogen incandescent lamp sold by Newport under reference number 6335. This lamp emits infrared electromagnetic radiation in the range of 750 nm to 2500 nm.

[0134] In one embodiment of the analyzer 1, the collimation lens 126 is sold by Newport under reference number KBX139.

[0135] In one embodiment of the analyzer 1, the second excitation source 132 consists of a plurality of LEDs. There are seven LEDs in total, of which four are first LEDs that emit electromagnetic radiation at a wavelength of 275 nm and are sold by HTDS under reference number CUD7GF1B. One second LED emits electromagnetic radiation at a wavelength of 338 nm and is sold by HTDS under reference number CUD4AF1B. One third LED emits electromagnetic radiation at a wavelength of 285 nm and is sold by HTDS under reference number CUN8AF1B. One fourth LED emits electromagnetic radiation at a wavelength of 420 nm and is sold by Roithner under reference number LED420-01. All LEDs can be fixed onto a factory-made support 136.

[0136] In one embodiment of the analyzer 1, a collimation lens can also be used in combination with a second excitation source 132. Such a collimation lens is sold by Edmund Optics under reference number 49556.

[0137] In one embodiment of the analytical apparatus 1, the first acquisition means 124 consists of an avaspec-2048XL spectrometer sold by Optoprim.

[0138] In one embodiment of the analytical apparatus 1, the second acquisition means 134 consists of a ULS-2048L spectrometer sold by Optoprim.

[0139] In one embodiment of the analytical apparatus 1, the reservoir 110 is equipped with a sample detector window designated WW10530-B by Thorlabs. The reservoir 110 may also be equipped with an presence detector designated VCNL4040M3OE by Mouser. Such equipment items make it possible to improve the automation of the analytical method according to the present invention.

[0140] In one embodiment of the analyzer 1, a temperature sensor can be equipped in the reservoir 110. The temperature sensor may consist of a temperature-capturing window sold by Thorlabs under reference number WW70530. Another suitable temperature sensor is sold by Mouser under reference number MLX90614ESF-ACC-000-SP. Temperature knowledge can be very useful for controlling sample progression.

[0141] "Examples of actual implementation forms of the present invention method" Referring to Figure 6a, the raw spectrum (solid line) obtained in step B) by applying the method according to the present invention is compared with the raw spectrum (dotted line) obtained by fluorescence spectroscopy using a reference method known from the prior art. The sample for this is barley, provided in the form of grains. The excitation wavelength used to perform these measurements is fixed at 340 nm. As can be seen in Figure 6a, it is clear that the signal / noise ratio of the raw spectrum obtained by the reference method is not as important as that of the raw spectrum obtained in step B) by applying the method according to the present invention.

[0142] Figure 6b shows the results of applying a Gaussian digital filter, the purpose of which is to filter out the electron noise present in the signal from the raw spectrum (solid line) obtained during step B) by applying the method according to the present invention, and from the raw spectrum (dotted line) obtained by fluorescence spectroscopy using a reference method known from the prior art.

[0143] Furthermore, Figure 6c shows the excellent reproducibility of fluorescence measurements performed during the implementation of the method according to the present invention on the same sample. This is clearly superior to the reproducibility that can be obtained by performing the same measurements using the reference method (Figure 6d) and this method, despite the prior application of digital filters. The very clear advantage in measurement reproducibility is explained by the optimization at the acquisition level of the signal / noise ratio of the spectra of all spectral components, which is made possible by the implementation of the method according to the present invention.

[0144] Figures 6e and 6f show that this results in a significant difference in the residuals measured relative to the mean spectrum according to the method performed. By applying the method of the present invention, the variability of the residuals is reduced, and the discrepancies between residuals in each replicate are reduced.

[0145] Referring to Figures 7a to 7f, it can be seen that the same conclusion applies when the excitation wavelength is 385 nm.

[0146] The following table summarizes the results shown in Figures 8a, 8b, and 9. In Figures 8a and 8b, 204 flour samples were measured on the same instrument (separately, as in the prior art) using an infrared module on one side and a fluorescence module on the other. The following figure shows a calibrated regression obtained by relating the values ​​measured by the reference method for each sample on the horizontal axis and the least-squares regression of infrared fluorescence or the predicted values ​​from cross-validation from multiple linear regression of fluorescence spectroscopy on the vertical axis, the latter of which is itself composed of PARAFAC resolution scores.

[0147] [Table 1]

[0148] Abbreviation: - RMSEC stands for "Root Mean Squared Error of Calibration". - RMSEVC stands for "Root Mean Square Error of Cross-Validation," - RMSEP stands for "Root Mean Squared Error of Prediction".

[0149] Table 1 shows a clear improvement in calibration error, accompanied by a decrease in external predictions when the two techniques are performed separately, a decrease that is observed in cross-validation when combined. However, this can be attributed to a slight overmodeling during calibration.

[0150] In both cases, thanks to the combination of infrared spectroscopy and fluorescence spectroscopy, an improvement of more than three times the performance of external predictions is observed.

[0151] The embodiments shown in the figures above are merely possible examples of the present invention and are not limiting in any way; rather, the present invention includes embodiments and design variations within the scope of those skilled in the art. [Explanation of Symbols]

[0152] 1. Apparatus for analyzing samples 100 measurement modules 110,410 Reservoir 140 optical elements 200 processing modules 300 Communication Networks 400 sample retention system

Claims

1. An apparatus (1) for analyzing a heterogeneous sample (S), wherein the apparatus (1) - Measurement module (100), - Processing module (200), Equipped with, The measurement module (100) is ○ A reservoir (110, 410) configured to accommodate the sample (S), and having a first wall (112, 422) and a second wall (114, 432) facing the first wall, ○ Electromagnetic radiation in the infrared field and / or near-infrared field (E Ｓ１ The reservoir is configured to emit infrared electromagnetic radiation (E) to the first wall (112, 422), and the first wall (112, 422) is configured to emit infrared electromagnetic radiation (E) Ｓ１ A first excitation source (122) that is transparent to ) and a transmittance spectrum (S ｉＲ S ｉ A first infrared spectroscopic subassembly (120) comprising a first means (124) for obtaining ) ○ Electromagnetic radiation in the ultraviolet field and / or visible field (E Ｓ２ At least one second excitation source (132) configured to emit the electromagnetic radiation (E) to the second wall of the reservoir, wherein the second wall (114, 432) is configured to emit the electromagnetic radiation (E) Ｓ２ At least one second excitation source (132) is transparent to the fluorescence spectrum (S) of the sample (S), such that the volume of the sample (S) that can be illuminated by the first excitation source (122) is at least partially equal to the volume of the sample (S) that can be illuminated by the second excitation source (132), and the fluorescence spectrum (S) of the sample (S) ｆ１ , S ｆ２ A second fluorescence spectroscopic subassembly (130) comprising a second means (134) for obtaining ) It is equipped with, The first sub-assembly (120) includes a diffusive transparent optical element (140) for electromagnetic radiation (E Ｓ１ ) emitted by the first excitation source (122). The optical element (140) receives electromagnetic radiation (E) emitted by the second excitation source (132) 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 acquisition means (124). Ｓ２ Outside the optical path of (E), and the electromagnetic radiation (E) emitted by the second excitation source (132) Ｓ２ Positioned outside the solid angle to collect the fluorescence signal emitted by the sample (S) when the sample is exposed to the ) The processing module (200) is connected to the measurement module (100) by a communication network (300) and includes a processor (220) configured to analyze data obtained by infrared spectroscopy and fluorescence spectroscopy. Apparatus (1) characterized by the following.

2. The apparatus (1) according to claim 1, wherein the optical element (140) constitutes the first wall (112, 422) of the reservoir.

3. The apparatus (1) according to claim 1 or 2, wherein the first wall (112, 422) of the reservoir is movable along an axis (X1) perpendicular to a plane (P1) passing through the first wall (112, 422).

4. The two walls (114, 432) of the reservoir (110, 410) are protected from electromagnetic radiation (E) emitted by the second excitation source (132). Ｓ２ The apparatus (1) according to any one of claims 1 to 3, which is anti-reflective against ).

5. The apparatus (1) according to any one of claims 1 to 4, wherein the second excitation source (132) is positioned between the second wall (114, 432) and the first acquisition means (124).

6. The apparatus (1) according to any one of claims 1 to 5, wherein the second acquisition means (134) and the axis (X') passing through the central plane and substantially perpendicular to the second wall (114) of the reservoir form an angle α with respect to the axis (X) passing through the first excitation source (122) and the second acquisition means (134).

7. The first excitation source (122) emits broadband polychromatic electromagnetic radiation (E Ｓ１ The apparatus (1) according to any one of claims 1 to 6, wherein the first excitation source (122) is a high-power halogen incandescent source, and the apparatus (1) emits ) and the first excitation source (122) is a high-power halogen incandescent source.

8. The second excitation source is monochromatic electromagnetic radiation (E Ｓ２ The apparatus (1) according to any one of claims 1 to 7, wherein the second excitation source (132) emits a light, and the second excitation source (132) consists of one or more LEDs.

9. Apparatus (1) according to any one of claims 1 to 8, comprising a housing for receiving a system (400) for holding the sample, the housing having an inner surface in which the holding system (400) is in contact with.

10. The apparatus (1) according to claim 9, comprising a system (400) for holding the sample, The holding system (400) is, a) A reservoir (410) comprising a first glass-fitted portion (420) having the first wall (422) and a second glass-fitted portion (430) having the second wall (432), wherein the first glass-fitted portion (420) is detachably attached to the second glass-fitted portion (430), b) A support block (450) comprising a connecting portion (460) and a base (454) that positions the holding system (400) and forms a bent portion together with the connecting portion (460) within the device (1), c) A removable part (470) comprising a housing (472) for receiving the reservoir (410), wherein the second glass-fitted part (430) is fixed to the removable part (470), and the removable part (470) is detachably connected to the connecting part (460), d) A connecting portion (480) having an opening (482), The connecting portion (480) is pivotable on the support block (450) and can move from an attachment position away from the removable portion (470) to a usage position where it is folded onto the removable portion (470) and the opening (482) faces the reservoir (410). The connecting portion (480) is provided with compressible means (486a, 486b, 488a, 488b) that, when the connecting portion (480) is in the use position, abut against the inner surface of the housing of the measuring module (100) that receives the holding system (400), thereby enabling contact positioning of the holding system (400). The apparatus (1) according to claim 9, comprising the above.

11. A method for analyzing a heterogeneous sample (S) using the apparatus (1) described in any one of claims 1 to 10, the method comprising the following steps, namely: A) The transmittance spectrum (S) of the sample (S) in the first infrared spectroscopy subassembly (120) ｉ The steps to obtain ) and B) The fluorescence spectrum (S) of the sample (S) in the second fluorescence spectroscopy assembly (130) ｆ１、 S ｆ２ The steps to obtain ) and C) A step of analyzing data obtained by infrared spectroscopy and fluorescence spectroscopy using a processing module (200), wherein a processor (220) is configured to determine at least one criterion for characterizing the sample from the data arriving from the analysis. D) A step of constructing a linear regression or nonlinear model by combining data obtained by infrared spectroscopy and fluorescence spectroscopy at the spectral level using the processing module, by concatenating pre-processed spectra and by associating scores derived from the decomposition of each spectrum, in order to obtain calibration of descriptive criteria for the condition of a sample, such as technical, sensory, nutritional, and hygienic quality standards. A method characterized by including

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