WO2017137805A1 - Systèmes et procédé de mesure quantitative de constituants de liquide - Google Patents

Systèmes et procédé de mesure quantitative de constituants de liquide Download PDF

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Publication number
WO2017137805A1
WO2017137805A1 PCT/IB2016/050723 IB2016050723W WO2017137805A1 WO 2017137805 A1 WO2017137805 A1 WO 2017137805A1 IB 2016050723 W IB2016050723 W IB 2016050723W WO 2017137805 A1 WO2017137805 A1 WO 2017137805A1
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WIPO (PCT)
Prior art keywords
sample
assay
collection surface
optical
aerosol
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PCT/IB2016/050723
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English (en)
Inventor
Hans Villemoes Andersen
Henrik Vilstrup Juhl
Original Assignee
Foss Analytical A/S
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Publication date
Application filed by Foss Analytical A/S filed Critical Foss Analytical A/S
Priority to PCT/IB2016/050723 priority Critical patent/WO2017137805A1/fr
Publication of WO2017137805A1 publication Critical patent/WO2017137805A1/fr

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02Food
    • G01N33/14Beverages
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N2021/3595Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/84Preparation of the fraction to be distributed
    • G01N2030/8447Nebulising, aerosol formation or ionisation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/12Circuits of general importance; Signal processing
    • G01N2201/129Using chemometrical methods

Definitions

  • the present invention relates to a system for and method of optical
  • spectrophotometric assay of components of a liquid sample in particular low concentration, non-volatile components.
  • characteristic wavelengths will lie in that portion of the electromagnetic spectrum from the ultra-violet, through the visible and into the infra-red regions (Optical radiation') and notably in the infrared region, particularly the mid-infrared region, of the electromagnetic spectrum.
  • the characteristic wavelengths will depend on the nature of the chemical bond itself, for example a Carbon-Hydrogen, a Carbon-Oxygen or a Carbon-Carbon bond, and also upon its environment (for example, its location within the liquid matrix). Thus a given molecule may result in absorption at several characteristic wavelengths. The amount of optical radiation absorbed at these characteristic wavelengths is proportional to the amount of the molecule being examined.
  • the spectrophotometer By subjecting the liquid sample to optical radiation comprising some or all of these characteristic wavelengths the spectrophotometer will generate a spectrum containing features that are characteristic of components present in said sample.
  • the generated optical spectrum contains information useful in identifying and quantifying components of interest in the liquid.
  • This technique has found application in the food and beverage industries where components in a liquid matrix, such as a wine, a milk or other potable product such as beer and fruit juices, are assayed using typically their interaction with infrared,
  • optical spectrophotometer based assay systems for one or both of the quantitative and the qualitative determination of components of a liquid sample.
  • assay systems comprise a monochromator or an interferometer based spectrophotometer for generating optical spectral data from the interaction of optical radiation with a liquid sample.
  • the spectrophotometer is configured with an inspection zone for receiving a sample for assay; an optical radiation source configured to supply optical radiation into the inspection zone to impinge on the received sample and a complementary detector for detecting optical radiation after it having impinged on and thus interacted with the received sample.
  • a data processor is provided in operable connection with the spectrophotometer to receive the spectral data and to process it using standard chemometric techniques in order to make therefrom at least a qualitative but preferably a quantitative determination of one or more components of the liquid sample to be assayed.
  • a broadband infrared Fourier transform interferometric spectrophotometer is employed in the assay of milk, particularly in the quantitative determination of urea in milk from the application of a chemometric model to infrared absorption data acquired in the wavelength region from 10.0 micrometers to 2.50 micrometers.
  • containing the components of interest for assay may often create an interfering background absorption signal and it is therefore desirable to separate at least a portion of the interfering liquid matrix from the components to be assayed.
  • FIG. 1 Another sample concentrator used in a spectrophotometer assay system is disclosed in EP 2009437 and comprises a freezer.
  • Water and similarly volatile components are frozen out from a water containing potable sample such as wine or milk to leave behind a liquid sample for assay having a higher concentration of relatively non-volatile components than the original water containing liquid sample.
  • freezing generally takes a relatively long time and a separation step is necessary to remove the frozen material from the sample to be assayed.
  • a further sample concentrator used in a spectrophotometer based assay system is described by N.K. AFSETH et al. "Predicting the Fatty Acid Composition of Milk: A Comparison of Two Fourier Transform Infrared Sampling Techniques"; Applied Spectroscopy 2010, vol. 64, no. 7 p.700- 707.
  • liquid milk samples diluted with water in a milk:water ratio of 75:25, are deposited in sample well plates and dried for approximately one hour at room temperature in an exicator using silica gel.
  • the resulting dry film samples were suitable for analysis using a Fourier Transform Infrared ('FTIR') analyser in transmission mode.
  • 'FTIR' Fourier Transform Infrared
  • a system for the optical spectrophotometric assay of components in a liquid sample comprising an optical spectrophotometer having an inspection zone for receiving a sample for assay, a radiation source configured to generate optical radiation for supply into the inspection zone to impinge on and thereby interact with the received sample for assay and a complementary detector for detecting an intensity of optical radiation after it having interacted with the received sample for assay; the system further comprising a concentrator for concentrating non-volatile components of the liquid sample wherein the concentrator comprises a nebulizer configured to discharge an aerosol of the liquid sample and wherein the system further comprises a collection surface spaced apart from the nebulizer and disposed to receive discharged aerosol to form the sample for assay.
  • a thin layer of sample liquid droplets may be deposited for evaporation on the collection surface which may either be located in or external of the inspection zone, the former location reducing the amount of handling of the sample required before assay. Evaporation of at least a portion of the more volatile components, including in some cases the liquid matrix, leaves behind a sample for assay that comprises a relatively high concentration of non-volatile components of the liquid sample distributed evenly in a thin, reproducible layer.
  • the liquid sample may be a water based sample, such as a wine, a milk or other potable product such as beer and fruit juices, and the system adapted for the mid-infrared optical assay of the water based liquid sample.
  • a water based sample such as a wine, a milk or other potable product such as beer and fruit juices
  • the collection surface may be formed of a
  • the collection surface may be formed of a reflective material, such as gold deposited onto the collection surface, to receive the discharged aerosol.
  • the optical radiation may pass through the sample for assay to be reflected from the reflective collection surface to pass through the sample for assay again before being incident on the detector. The amount of sample interacted with the optical radiation is therefore effectively doubled which can increase the accuracy of the assay or reduce the time needed to deposit sufficient sample on the collection surface.
  • a plurality of such collection surfaces located, spaced apart, on a support, such as a planar or disc-like support.
  • a support such as a planar or disc-like support.
  • the concentrator further comprises a housing
  • a heater for example as may be formed using a resistive heater element or an infra-red radiation source, may be provided in some embodiments and is configured to supply heat to the collection surface. This speeds up the evaporation process.
  • a method of spectrophotometric assay of components in a liquid sample comprising the steps of: generating an aerosol of the liquid sample;
  • the optical spectrophotometric assay is a mid-infrared spectrophotometric assay.
  • the step of allowing liquid to evaporate from the aerosol may, in some applications of the method, include supplying heat to the collection surface. This enhances the rate of evaporation of liquid from the aerosol.
  • FIG. 1 A schematic representation of one embodiment of a system
  • FIG. 2 A schematic representation of another embodiment of a
  • Fig. 3 Illustrates a nebulizer of the venturi type for use in a system
  • Fig. 4 Illustrates a nebulizer of the ultrasound type for use in a
  • Fig. 5 Shows comparative transmission mid-infrared spectra of milk
  • Fig. 6 Shows C) a reflection mid-infrared spectrum of milk obtained
  • FIG. 1 One embodiment of a system for the optical spectrophotometric assay of components in a liquid sample is illustrated in Fig. 1.
  • the system 2 comprises an optical spectrophotometer 4 and a concentrator 6.
  • the optical spectrophotometer 4 of the present embodiment comprises a Fourier Transform (FT) interferometer 8 and includes a radiation source 10 configured to generate optical radiation.
  • the radiation source 10 is here illustrated as being contained within the interferometer 8 but in other embodiments it could be provided external of the interferometer 8 and the optical radiation it generates directed towards the interferometer 8, for example via a fiber optic or lens system.
  • the FT interferometer 8 is constructed to operate in a manner well known in the art and thus comprises a beam splitter 12 on to which, in use, optical radiation generated by the radiation source 10 is initially supplied to be split into two beams, a first beam which is reflected by the beamsplitter 12 to travel towards a first mirror 14 and a second beam which is transmitted through the beamsplitter 12 to travel towards a second mirror 16.
  • One or both of the first mirror 14 and the second mirror 16 (here illustrated as being the second mirror 16) is movable along the direction of propagation of the respective first and or second beam.
  • Optical radiation is reflected from the first mirror 14 and the second mirror 16 to recombine at the beamsplitter 12 and pass through an inspection zone 18 into which, in use, a sample for assay 40a is received so that the recombined optical radiation from the beamsplitter 12 impinges on and interacts with it.
  • a detector 20 is provided to detect optical radiation after it having passed through the inspection zone 18 and is configured to monitor wavelength dependent intensity variations of the incident optical radiation and to transmit a signal representative of the monitored intensity variations to a data processor 22, here illustrated as being located external of the FT interferometer 8.
  • the data processor 22 may be located at a remote location and connected to the detector 20 via a
  • the detector 20 may additionally or alternatively be located remote of the FT interferometer 8 and the optical radiation communicated to it via fiber optics.
  • the data processor 22 is, in a manner well known in the art, configured to apply to the signal passed from the detector 20 of the optical
  • spectrophotometer 4 a chemometric model linking a component of interest to be assayed in the liquid sample with wavelength dependent intensity variations and thereby obtain a prediction of a quantitative measure of the component of interest in the liquid sample.
  • the concentrator 6 comprises a nebulizer 24 for generating and
  • a support 30 is provided as an element of the system 2 and has a number of sample collection surfaces 32 (illustrated as one surface) at which the sample for assay 40a will be formed.
  • this one or more collection surface 32 is translucent to optical radiation generated by the source 10, at least for those wavelengths sensitive to components of the liquid sample to be assayed, the
  • This translucent collection surface 32 may, for example, be formed of a calcium fluoride disk in embodiments of the system 2 adapted for mid-infrared spectrophotometric assay.
  • the support 30 may be releasably located in a holder (not shown) or, when present, releasably located on the heater plate 26 (as illustrated) so as to be able to receive (at least on the collection surface 32) liquid sample aerosol which, in use, is discharged from the nebulizer 24. In other embodiments the support 30 may be dispensed with.
  • the collection surface 32 may be divided to provide different sections, each of which may act as a separate collection surface for receiving a different sample aerosols.
  • the support 30 When located in the inspection zone 18 the support 30 may be movable so that the optical radiation passing through the measurement zone 18 can impinge on and interact with different portions of the collection surface 32 (or indeed with different collection surfaces should the support 30 be provided with more than one) on which the sample for assay 40a has been deposited. In this manner a plurality of quantitative measures of the component of interest can be made using different aliquots of the sample for assay or the component of interest in a plurality of different samples (each being deposited as a different sample for assay on its own associated sample collection surface) may be measured.
  • an optical radiation passing through the measurement zone 18 can impinge on and interact with different portions of the collection surface 32 (or indeed with different collection surfaces should the support 30 be provided with more than one) on which the sample for assay 40a has been deposited.
  • the support 30 may be a disc having a plurality of separate collection surfaces 32 located circumferentially separated around the disc.
  • a rotary motor (not shown) may then be provided as an element of the optical spectrophotometer 4 to rotate the disc 30 between measurements to move a different collection surface 32 into the path of the optical radiation passing through the inspection zone 18.
  • a reflective surface such as a gold surface when mid- infrared optical radiation source 10 is employed.
  • the detector 20 is then located, for example as illustrated by the broken construction 20', to detected optical radiation that has passed through the sample for assay 40a twice as a result of being reflected from the reflective collection surface 32.
  • the housing 28 of the present embodiment is configured with an interior space 48 for containing the collection surface 32, the nebulizer 24 (or at least the portion at which the aerosol is generated) and, where present, the heater plate 26.
  • a pressurised gas (typically air) supply 50 is connected to the interior space 48 for generating an overpressure therein.
  • a pressure release valve 52 may also be provided in connection with the interior space 48 for safety. This pressurised housing 28 helps prevent dust from the surroundings becoming entrained in the aerosol and thus from contaminating the collection surface 32.
  • the nebulizer 24 of the present embodiment is provided with a gas inlet 34 for connection to a pressurised gas (typically air) supply 36 and a liquid inlet 38 for connection to a supply of liquid sample 40 to be assayed.
  • the nebulizer 24 is here illustrated by way of example as being of a venturi (or so-called 'airbrush') type and is thus configured to, in use, pass a stream of fast moving pressurised gas from supply 36 past a venturi which is provided in liquid connection with the inlet 38 (or in some embodiments a local reservoir of the liquid 40 to be assayed connected to supply of the same).
  • This aerosol 44 is discharged from a spray nozzle 42 of the nebulizer 24 towards the collection surface 32.
  • FIG. 3 An example of such a venturi type nebulizer 24 is illustrated in Fig. 3 and comprises a coaxial arrangement of outer gas conduit 24a intended for connection to gas inlet 34 and an inner liquid sample conduit 24b intended for connection with liquid inlet 38.
  • Each of the gas conduit 24a and the liquid sample conduit 24b terminate in the spray nozzle 42.
  • the liquid sample conduit 24b is terminated in the spray nozzle 42 with a small diameter venturi opening 24c and the gas conduit 24a terminates in the spray nozzle 42 with a section 24d shaped to direct a flow of gas across the venturi opening 24c in order to suck liquid there through and thereby to generate the aerosol 44 for discharge from the spray nozzle 42.
  • a pump here a
  • piston pump 46 is provided in liquid communication between the supply of liquid sample 40 to be assayed and the inlet 38 to the nebulizer 24 to provide a pressurised feed of liquid to the venturi opening 24c. This has an advantage that the flow of liquid through the venturi opening 24c can be better controlled than if only the gas pressure from supply 36 is regulated.
  • FIG. 2 Another embodiment of a system for the optical spectrophotometric assay of components in a liquid sample is illustrated in Fig. 2.
  • the system 60 of Fig. 2 comprises an optical spectrophotometer 62 and a concentrator 64.
  • the optical spectrophotometer 62 is in the present embodiment illustrated as a conventional monochromator here having a fixed dispersion element 66 for generating a spatially dispersed spectrum 68 which is incident on diode array detector 70.
  • the diode array 70 is configured with an array of individually addressable detector elements, each of which will receive a different wavelength portion of the spatially dispersed spectrum 68 and will generate a signal representative of wavelength dependent intensity variations for transmission to a data processor 72.
  • the data processor 72 is configured, as per the data processor 22 of the
  • Fig. 1 to apply an appropriate chemometric model to the transmitted signal in order to determine a quantitative measure of a component of interest.
  • the concentrator 64 comprises a nebulizer 74 for generating and
  • the nebulizer 74 is, in use, connected to a source of liquid sample for assay 80 via an inlet 77 and to a source of pressurised gas 76 via an inlet 75.
  • the collection surface 84 is here illustrated, by way of example only, as an outer surface of a conventional Attenuated Total internal Reflection (ATR) crystal 86 which is located in thermal connection with the heater plate 82 in an inspection zone 88 associated with the optical spectrophotometer 62.
  • ATR Attenuated Total internal Reflection
  • a radiation source 90 is provided to generate optical radiation having
  • optical radiation undergoes total internal reflection within the ATR crystal 86 to be reflected at least once from the surface 84 onto which the layer 92 has been formed.
  • the optical radiation which has traversed the ATR crystal 86 is focussed onto an entrance slit of the monochromator constituting the spectrophotometer 62.
  • the nebulizer 74 here is of the ultrasound type generally known in the art, such as is illustrated in Fig. 4.
  • the nebulizer 74 comprises a piezoelectric crystal 74a for generating ultrasound waves into a buffer solution 74b which provides for efficient coupling thereof into a reservoir 74c of liquid sample.
  • the reservoir 74c is connectable to the source of liquid sample 80 via inlet 77 and is provided with a narrow opening 74d through which liquid droplets 74e are ejected by the ultrasound into a chamber 74f.
  • the chamber 74f is connectable at a first end 74g to the inlet 75 for the pressurised gas source 76 and terminates at a second end in a spray nozzle 74h through which the liquid droplets 74e entrained in a gas stream from the pressurised gas source 76 will be discharged as the aerosol 78.
  • the systems according to the present invention may be usefully employed in the assay of low concentration non-volatile components of water based liquid samples such as a wine, a milk or other potable product such as beer and fruit juices.
  • the radiation sources 10, 90 are then mid-infrared radiation sources and the spectrophotometers 4, 62 are mid-infrared spectrophotometers.
  • FIG. 5 An example of a mid-infrared transmission spectrum obtained for a milk sample 40 using a system according to Fig. 1 is shown at Fig. 5 as the upper trace A.
  • a concentrated layer 40a of 37 micrometers (microns) thickness is built up on the translucent collection surface 32 of the planar support 30 and introduced into the inspection zone 18 of the FT
  • the transmission spectrum A is that recorded by detector 20.
  • the transmission spectrum A shows features around 1600 cnv 1 and around 3000-3500 cnr 1 which are regions of 'noise' in the spectrum B. It is known that urea and beta-hydroxybutyrate both produce absorbances around the 1600 cnr 1 region and that Cis-double bond is responsible for absorbances around 3000-3500 cnr 1 . Since these features are better distinguished in the spectrum A, obtained from a concentrated layer 40a which is generated by the system according to the present invention, it is expected that a quantitative measure of the aforementioned components of the milk sample 40 may be better made using a system according to the present invention.
  • the spectrum A is 'lifted' relative to the spectrum B i.e.
  • the system according to the present invention produces generally higher absorbance values. This is probably due to some scatter of the dried sample layer 40a: some of the light is scattered away from the detector 20. Without this 'lifting' it can be seen that the actual peak heights are similar - which is to be expected since both the concentrated layer 40a and the liquid sample comprise the same amount of non-volatile component, although the thickness of the concentrated layer 40a is much less than that of the liquid milk aliquot.
  • FIG. 6 An example of a mid-infrared reflection spectrum obtained for the same milk sample 40 using a system according to Fig.1 adapted to make reflection measurements on a 37 micron layer of a sample for assay 40a located in the inspection zone 18 is shown at Fig. 6 as the upper trace C.
  • a transmission spectrum D is shown for comparative purposes. Again it can be seen that the reflection spectrum C exhibits features around 1600 cnr 1 and around 3000-3500 cnr 1 which are not distinguishable in the spectrum D. Moreover it can be seen that the signal at the detector 20' is almost twice that measured by the detector 20 in transmission.
  • a 'concentration factor' may be provided which links the quantitative measure obtained using the present system (i.e. after evaporation) to the amount present in the original liquid sample.
  • This factor may be obtained in many ways, such as, for example:
  • concentration factor can be individual.
  • FFA concentration in milligrams per gram
  • Figs. 7 and 8 Measurements were made using the system according to the present invention on a milk sample set having had reference analysis made for urea content.
  • Fig. 7 represents a conventional full spectrum PLS calibration established using cross validation based on measurements on the system according to the present invention on the milk sample set using two replicates. Variation in the thickness of the deposited layers between samples of sample set are corrected for using a fat absorption peak relative to the same peak using the conventional system.
  • Fig. 8 represents a conventional full spectrum PLS calibration established using cross validation based on
  • the Root Mean Squared Error of Prediction (RMSEP) for the calibration of Fig. 7 is 8.7 whilst the RMSEP for the calibration of Fig. 8 is 30.3. This indicates an accuracy
  • nebulizers of known type for generating aerosols can be substituted for those disclosed herein and the nebulizers disclosed herein can be interchanged without departing from the invention as claimed.
  • Other mid-infrared spectrophotometers can be substituted for those disclosed herein and those disclosed herein can be interchanged without departing from the invention as claimed.
  • the mid-infrared spectrophotometer may be substituted with spectrophotometer operating in any optical wavelength range appropriate for the absorption by nonvolatile components of interest in the liquid sample.
  • the collection surface may be provided in other ways, for example a solid opaque plate may be used. Also equivalent or complementary
  • spectrophotometer methodologies such as reflection or absorption in place of transmission
  • heater arrangements other than the resistive element heater plate type illustrated such as infrared radiant heaters, are intended to fall within the scope of the invention as described and as claimed.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Analytical Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Food Science & Technology (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne un système (2) permettant l'analyse spectrophotométrique optique de constituants d'un échantillon liquide (40), qui comprend un spectrophotomètre optique (4) ayant une zone d'inspection (18) destinée à recevoir un échantillon à analyser (40a) ; une source de rayonnement (10) configurée pour générer un rayonnement optique à fournir dans la zone d'inspection (18) destiné à arriver sur un échantillon à analyser (40a) reçu et, de ce fait, interagir avec ce dernier ; et un nébuliseur (24) conçu pour évacuer un aérosol (44) de l'échantillon liquide (40) vers l'une parmi une ou plusieurs surfaces de collecte (32) éloignées du nébuliseur (24) et disposées pour recevoir l'aérosol (44) évacué pour former l'échantillon à analyser (40a).
PCT/IB2016/050723 2016-02-11 2016-02-11 Systèmes et procédé de mesure quantitative de constituants de liquide WO2017137805A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252829A (en) 1992-03-25 1993-10-12 A/S Foss Electric Method of determining urea in milk
US6885003B1 (en) 1999-08-19 2005-04-26 Foss Electric A/S Method and device for objective qualitative analysis of grape must and/or wines using wideband infrared spectrometry
WO2005099404A2 (fr) * 2004-04-08 2005-10-27 Aradigm Corporation Procede d'analyse de produits chimiques deposes au moyen d'un systeme de distribution de produits chimiques
EP2009437A1 (fr) 2007-06-26 2008-12-31 FOSS Analytical A/S Dispositif et procédé pour l'analyse d'un liquide de vinification
US20100261280A1 (en) * 2005-07-14 2010-10-14 Black Rodney S Biological and chemical monitoring

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252829A (en) 1992-03-25 1993-10-12 A/S Foss Electric Method of determining urea in milk
US6885003B1 (en) 1999-08-19 2005-04-26 Foss Electric A/S Method and device for objective qualitative analysis of grape must and/or wines using wideband infrared spectrometry
WO2005099404A2 (fr) * 2004-04-08 2005-10-27 Aradigm Corporation Procede d'analyse de produits chimiques deposes au moyen d'un systeme de distribution de produits chimiques
US20100261280A1 (en) * 2005-07-14 2010-10-14 Black Rodney S Biological and chemical monitoring
EP2009437A1 (fr) 2007-06-26 2008-12-31 FOSS Analytical A/S Dispositif et procédé pour l'analyse d'un liquide de vinification

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. CHILLA ET AL.: "Automated on-line-solid-phase extraction-high-performance liquid chromatography-diode array detection of phenolic compounds in sherry wine", JOURNAL OF CHROMATOGRAPHY A, vol. 750, no. 1 -2, 1996, pages 209 - 214, XP004069757, DOI: doi:10.1016/0021-9673(96)00557-2
N.K. AFSETH: "Predicting the Fatty Acid Composition of Milk: A Comparison of Two Fourier Transform Infrared Sampling Techniques", APPLIED SPECTROSCOPY, vol. 64, no. 7, 2010, pages 700 - 707, XP055289821, DOI: doi:10.1366/000370210791666200

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