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    • 专利摘要:
    Invention Patent: "MEASUREMENT DEVICE AND PROCESS TO ANALYZE A TEST GAS THROUGH INFRARED ABSORPTION SPECTROSCOPY".The inversion refers to a measuring device for analyzing a test gas by means of infrared absorption spectroscopy.The measuring device has: a measuring chamber (2) with the gas to be analyzed, a laser (1), which is so arranged in relation to the measuring chamber (2) that the light emitted by the laser passes through the chamber measuring device (2), a shielding device (61), which detects the light emitted by the laser (1) and which passes through the measuring chamber (2), and an evaluation unit (8), which evaluates the signals generated by the detection device (61), with respect to an absorption of light in the measuring chamber (2). It is foreseen that the laser (1) is a laser that emits in narrow band, whose line width is less than or equal to the width of an infrared absorption line to be measured of the test gas, the laser (1) is formed and adjusted in such a way that the laser frequency is varied periodically within a defined spectral range, the laser frequency and the variation of the sameq being selected in such a way that at least one infrared absorption line to be measured from the gas The test is located in the defined spectral range, and the detection device (61) is formed and adjusted in such a way that it detects, with temporal resolution, the light emitted by the laser (1) and which passes through the measurement chamber (2), such that the absorption of light can be determined, with frequency resolution, within the defined spectral range, with the detection device (61) making a single absorption measurement within 10-5 s more quickly. In addition, the measuring device is suitable and adjustable to measure the breathing gas of a human or animal as a test gas, the respiratory gas being replaced in the measurement chamber only by the breathing of the person or animal and the respiratory resistance of the measuring device is less than 60 mbar.
    公开号:BR112012015680A2
    申请号:R112012015680-2
    申请日:2010-12-21
    公开日:2020-09-08
    发明作者:Karsten Heyne；Tom Rubin
    申请人:Humedics Gmbh；
    IPC主号:
    专利说明:

    . Invention Patent Descriptive Report for "DEVICE MEASUREMENT AND PROCESS TO ANALYZE A TEST GAS BY INFRARED ABSORPTION SPECTROSCOPY ".
    DESCRIPTION The present invention relates to a measuring device for analyzing a test gas by means of infrared spectroscopy according to the preamble of claim 1, as well as a corresponding process. It has been known for centuries that the smell of breathing can be an indicator of a possible disease. The most prominent example is the sweet-fruity smell caused by acetone in Type 1 Diabetes mellitus. Even the breathing of people Healthy products contain several hundred compounds, volatile chemicals, so-called “volatile organic compounds” (VOCs), in - small concentration (ranging from ppm to ppt). Some of them play an * 15 role in pathophysiological processes. If there is a disease, it increases the concentration of certain trace gases in the breath. In some diseases, gases that do not occur in the healthy body can also be proven. Therefore, respiratory gas analysis offers great potential for clinical diagnosis and monitoring of therapies. However, the trace gas concentration is often so small that it cannot be measured sufficiently accurately with the available gas analytical processes. There are highly sensitive verification processes, such as, for example, mass spectroscopy or FTIR spectroscopy in multi-pass test cells. However, these devices cannot be used directly on the patient and, therefore, are of no importance for clinical practice. This is also due to the fact that the evaluation takes several days and due to the transport of the sample, sources of incalculable errors occur. Mobile elements in the field of infrared absorption spectroscopy with diode lasers (eg lead salt lasers) as light sources have also been in use for several decades, but have so far not achieved stability needed by
    . a longer period for sensitive gas testing, so that, here, too, the use was limited to researching medicinal fundamentals.
    An alternative method is called the NDIRS process - (NDIRS -— Non-dispersive IR Spectroscopy). It proves density fluctuations in the test gas, which are caused by the absorption of infrared light.
    This verification process is sensitive and can take a measurement every two and a half minutes.
    However, the measurement results are adulterated by other gases, such as, for example, oxygen, so that this method can only be used to a limited extent in clinical practice.
    Another method is used by the company Oridion Systems Ltd. under the name BreathlDG.
    Here, a pressure lamp of. CO, as a light source.
    However, this method is severely limited in its sensitivity and speed by oscillations in line width that appear (in the lamp and in the test gas), small intensities of light and spectral fluctuations and, therefore, does not provide highly sensitive measurement results in no time.
    The NDIRS method and the Oridion Systems Ltd. method are well-suited, for example, for testing the Heliobacter pylori bacteria in the patient's stomach, the presence of the bacteria is qualitatively proven through an increased ** CO> content in the air of expiration, after the administration of a diagnostic agent marked "C.
    Qualitative testing processes lose their importance when the test is located in the same price segment as the treatment.
    Another strategy to ensure simple and quick proof of volatile chemical compounds is the use of sensitive surface microchips, which select and bind special trace gases from the respiratory air.
    As a result, sensitive evidence of volatile chemical compounds is possible and a qualitative decision can be made as to whether or not the patient is ill.
    The mere evidence of a disease is informative, however it still does not give any information about the appropriate therapy.
    For this reason, the future of respiratory gas analysis lies in the quantitative determination
    rative of the degree of illness, which provides the physician with direct auxiliary means of decision for therapy. When these tests can be performed simply and quickly and the results are immediately available to the doctor in an understandable way, the test can be effective in clinical practice. The requirements for quantitative respiratory gas tests are high: for the clear identification of trace gases, high selectivity and proof sensitivity is required, since, in most cases, the concentration is within the range of ppm up to ppb. Quantitative determination of the amount of trace gas must be guaranteed. In addition, measurements should take place online and in real time, to avoid a complex and error-prone sample collection (for example, in bags or in the side chain). For practical and economical use, they must be. easy handling, small size, robustness, low maintenance effort and / or a favorable cost-benefit ratio are required. These high and multiple requirements, Y currently, cannot be fully satisfied by any gas analytical process.
    Exhaled human air has a carbon dioxide volume ratio of 2% to 4% and is exhaled in 10 to 20 breaths, in babies and newborns up to 25 to 50 breaths per minute. The person's breathing pressure amounts to approximately 5 KPa (50 mbar), up to a maximum of 16 KPa (160 mbar), at a volume of approximately 0.5 liter. Of the breathing air, only approximately 70% reaches the lung, so that only approximately 70% of the gas volume is present in a markedly increased proportion of carbon dioxide. In the volume of gas remaining - the volume of dead space - the concentration of carbon dioxide can drop to the concentration of ambient air, approximately 0.04%. This leads to the fact that the concentration of carbon dioxide in the breathing air can fluctuate in two orders of size, from 0.04% to 4%. Concentrations of carbon dioxide above 5% are toxic and can lead, for example, to headaches and cramps.
    The amount of carbon dioxide produced depends on the individual metabolism of each individual person. Several products are used
    Approach procedures to assess a person's carbon dioxide production. The variables used there are, for example, weight and body surface. The body surface, in turn, is most often evaluated with body weight and size, so that medicine is often only possible to count on moderately accurate variables, which strongly limits or even makes it impossible a quantitative result assessment.
    For the direct quantitative determination of the metabolism or metabolization process, it is necessary to monitor the dynamics of the process with temporal resolution, in the best way, in real time. When the metabolism dynamics has a kinetics, which can be modeled by a first order differential equation (1st order dynamics), then. by solving the differential equation or by adapting an exponential function: y (l = A * exp (-Vtau) the maximum of the kinetics A and a. tau time constant are determined. The variables A and tau can then be quantitative determination of metabolic parameters.The activation of the metabolism dynamics is best achieved by a short temporal initiation, for example, the iv administration of a diagnostic agent or the release of a diagnostic agent due to exposure to When the release or the beginning of the dynamics lasts longer than the tau increase or more than a breath, then the dynamics of the release need to be determined separately and unfolded from the metabolic dynamics. rapid metabolization is the iv administration of the diagnostic agent 13C-metacetin in the bolus, which is distributed in the blood (about 60 heartbeats per minute) and arrives in approximately one second to the liver, where it is metabolized to p aracetamol and 13CO2. The onset of dynamics is much faster than the respiratory rhythm and thus leads to a first-order dynamic, which can be directly assessed. However, when 13C-metacetin is administered orally, the adsorption in the stomach leads to a doubling of the dynamics with the stomach adsorption dynamics, which significantly adulterates the dynamics. To follow the metabolism dynamics in real time,
    7 each breath must be measured with very high sensitivity. This means that the breathing air in the measuring chamber needs to be changed very quickly and that in less than two seconds a complete breath assessment must have taken place.
    An analysis process, which enables a quantitative determination of liver function, is described in WO 2007/000145 A2. The process is based on a substrate flood of the substrate to be metabolized in the liver and the determination of the maximum substrate conversion speed, which provides information on a patient's liver functioning capacity. From WO 2007/107 366 A1 there is known a device according to the genus for spectroscopic analysis of a gas, in which a measuring chamber can be continuously permeated with a test gas.
    * 15 The present invention is based on the task of perfecting the measurement device known from WO 2007/107 366 A1 and the measurement process used there, in order to be able to carry out measurements in real time.
    This task is solved according to the invention by a measuring device with the characteristics of claim 1 and a process with the characteristics of claim 32. Configurations of the invention are indicated in the secondary claims. According to them, the solution according to the invention provides for the use of a narrow-band laser emitter. As a narrowband emitting laser, it is considered a laser whose line width is selected in such a way that it is less than or equal to the width of the absorption line to be measured from the test gas to be measured. It is also foreseen that the laser frequency will be varied periodically within a defined spectral range, with the laser frequency and its variation being selected in such a way that at least one absorption line to be measured in the test gas is in the defined spectral range. The periodic variation in the laser frequency (also known as tuning) is
    "associated, in this case, with a defined spectral range, which is measured during each period of this frequency variation. In this spectral range there is at least one absorption line to be measured.
    It is also provided, according to the invention, that the detection device is formed and adjusted to detect, with temporal resolution, the light emitted by the laser and that passes through the measuring chamber, in such a way that the absorption of light can be determined, with frequency resolution, within the defined spectral range. In this case, the detection device performs a single absorption measurement within 10 seconds or faster, particularly within 10 seconds or faster. Through the rapid measurement, a spectral range can be detected, with frequency resolution, which is measured by the variation of the laser frequency. The measured spectral range is measured, in this chaos, with a plurality of measurement points, which correspond, in each case, to a measurement - 15 of absorption, for example, with 20, 100, 500 or 1000 measurement points.
    The high temporal resolution of the absorption measurements allows to detect, with frequency resolution, a spectral range, which is defined by the variation of the laser frequency and in which there is at least one absorption line to be measured, with a high density of individual measurement points within the spectral range. This is associated with several advantages. Thus, the high temporal resolution and the high point density of the measurement values obtainable thereby with a spectral range measured during a frequency variation, is associated with a high measurement accuracy. It is further increased when an average formation occurs over several spectra detected one after the other, as is predicted in a modality of modality.
    The high temporal resolution, the high spectral resolution (obtained by a high density of points of the individual measurements) and a high sensitivity allow to measure absorption lines with a sensitivity within the scope of ppb. Such sensitivity is essentially necessary, for example, to ensure that the measuring device is used for the quantitative verification of metabolized substrates.
    "In addition, the measuring device is particularly suitable and adjustable for the purpose of measuring the breathing gas of a human or animal as a test gas, the respiratory gas being exchanged in the measuring chamber only by the breathing of the human or of the animal and the breathing resistance of the measuring device is less than 6 KPa (60mbar), particularly less than 5 KPa (50 mbar) and, in a particularly preferred way, less than 4 KPa (40 mbar) That is, no pumps or other devices are needed to transport the test gas through the measuring device. Expressed in other words, the counter pressure formed by the measuring device amounts to less than 6 KPa (60 mbar), particularly me - in the case of 5 KPa (50 mbar) and, particularly preferably, less than 4 KPa (40 mbar). Such a small back pressure can be overcome - without technical assistance by a correspondingly high pressure (which is generated, for example, by the breath of a being h human or animal).
    15 When carrying out measurements in the passage of the test gas through the measuring chamber, it is also possible to detect, with high resolution, temporal changes in the composition of the test gas in real time. For example, it is possible to detect changes in isotope ratios in the respiratory gas, in real time, and this at concentrations of carbon dioxide in the respiratory gas in the range between 0.08% and 8%.
    In a configuration of the invention, it is provided that the laser frequency and its variation are selected in such a way that at least two lines of absorption of the test gas are located in the defined spectral range. This makes it possible, for example, to determine the relationship of two isotopes of the test gas through the absorption of light that occurred in two absorption lines. In the case of isotopes, these are, for example, COz and 12CO ,. As isotopes are designated not only atoms with the same ordinal number, but with a different mass number, but also molecules, which contain these different atoms. Instead of the ratio of two isotopes, the ratio of two elements (with different ordinal numbers) or two molecules can also be determined by means of two or more absorption lines.
    : The determination of the ratio of two isotopes, elements or molecules allows, in addition, the determination of absolute values of the respective isotopes, elements and molecules, also in the case of varying concentrations.
    For example, the determination of the CO content, in waste water, in the breathing, fluctuations in the concentration of CO, from 0.04% to 4%, occur. The oscillation measure can be detected by determining the absolute content of * COs (for example, by breathing). With this, the absolute content of the isotope ** CO>, which is in a natural, fixed relationship, for "CO.
    In addition, modifications can be detected, due to an additional metabolism of "* CO ,, through evaluation of the modification of the relationship of the two isotopes.
    The high resolution and dot density of the measuring devices according to the invention allows to determine the relationship of two isotopes, elements or molecules in real time.
    This is of particular interest when the relationship changes over time.
    In one configuration, a display device is associated with the evaluation unit, which represents a change in the relationship over time.
    The measuring device according to the invention can be formed without mirrors, with the light emitted by the laser passing through the measuring chamber exactly once.
    With this, a simple optical structure is made available and little susceptible to defects.
    Unlike in the measuring chamber of WO 2007/107 366 A1, there are therefore no mirrors in the measuring chamber, in which the laser light would be reflected multiple times.
    The measuring chamber has only an input window, through which the laser light enters the measuring chamber, and an exit window, through which the transmitted light exits the measuring chamber.
    In another configuration, the measuring device has means of regulating temperature (particularly heating means), which regulate, in particular, heat, the measuring chamber and existing windows to a constant temperature, which is located, for example, above 35ºC.
    This prevents water vapor, which may be present in the test gas, from fogging the measuring chamber.
    It is also
    : a cooling of the measuring chamber is possible.
    In another embodiment of the invention, the measuring chamber is intended to be permeated continuously or intermittently by test gas. For this purpose, the measurement chamber has, in a configuration, an open structure, without valves or ventilation valves, which could obstruct the flow of the test gas into and out of the measurement chamber. In addition, in a configuration, the maintenance device is expected to have, substantially, a cross section for the permeation of the test gas between the gas inlet in the maintenance device and the gas outlet in the maintenance device. . As a result, a laminar flow is made available at all points of the measuring device and prevents gas from accumulating at certain points and - it is not displaced by new test gas. In a variant, the measuring device has at least 7 15 sections, particularly within the entire measuring chamber, a constant cross section, so that, at least in parts, a laminar flow is guaranteed. on the measuring device. When, for example, the entire measuring chamber has a constant cross-section in operation, a laminar flow of the test gas is substantially guaranteed within the entire measuring chamber. With this, very precise measurements are made possible, in a particularly advantageous way.
    In another configuration, the test chamber is fed with test gas and the test chamber is flushed with test gas in one direction, which is perpendicular to the direction in which the light passes through the measuring chamber. This ensures that the gas supply and discharge, as well as corresponding connections, do not disturb the flare light. In this case, the gas supply and discharge are preferably alternately arranged so that the test gas flows partially in the direction of the laser beam through the measuring chamber.
    The measuring device is preferably formed in such a way that light detection with temporal resolution takes place by the detection device, during the passage of the test gas through the measuring chamber.
    | dition.
    Infrared absorption measurements are therefore carried out at each stage of the gas flow, particularly also when the test gas passes through the measurement chamber.
    Absorption measurements take place in the passage (therefore, in the passage measurement technique). In another configuration, the measuring device comprises a spirometer, which detects the volume flow of the test gas, which flows through the measuring chamber.
    In this case, it can be expected that the test gas will permeate the spirometer, after passing through the measurement chamber, in which case it exits, then through the spirometer of the measuring device. In principle, the spirometer may be arranged at any point between the gas inlet of the measuring device and the gas outlet of the measuring device therein. . The measurement of the volume current makes it possible to determine the total absolute quantities of certain molecules of a given - 15 quantity of gas, which corresponds, for example, to a breath of a human or animal.
    Particularly, the absorption can be determined directly, the concentration, since the extinction coefficient for each absorption line is known and also the length of the measuring chamber.
    As the absorption and the volume current, through the spirometer, can be monitored, with temporal resolution, in real time, the total amount can be determined in real time by integrating the volume product and concentration over time .
    In one configuration, an antechamber is also provided, through which the test gas flows into the measurement chamber.
    In that case, the —antechamber is preferably formed to heat or cool the test gas to a certain temperature and thereby reduce the water vapor content of the test gas.
    In another configuration, the antechamber is preferably formed, alternatively or additionally, to reduce the water vapor content of the test gas to at least 60% relative air humidity.
    The reduction of the water vapor content occurs, preferably, through semipermeable membranes, which allow, exclusively, an exchange of water vapor.
    'water (but not other substances). The air outside the membrane must have a relative air humidity of less than 50% relative air humidity. If the water vapor content outside the antechamber is less than inside, then the water vapor content of the test gas that permeates the antechamber is reduced. The total area of the membrane determines the amount of gas exchange that can occur.
    As an example, the application of the measurement device for breath analysis is mentioned, in which an individual breath (particularly a full breath) is examined. Air humidity in a breath often makes up more than 90% relative air humidity, which is reduced by the semipermeable membrane in the antechamber to less than 50% relative air humidity. The active area of the semipermeable membrane: in this case it can make up, for example, more than 150 in , particularly more than 200 cm , especially, more than 250 in .
    7 18 In another configuration, the antechamber is preferably formed, alternatively or additionally, to homogenize the test gas. The homogenization of the individual test gas occurs through several (at least two) branches of different length and diameter, which are permeated by parts of the test gas. After the branching region, the parts of the test gas are not assembled again. In this case, it is important that the total cross section of all branches (therefore the sum of the cross sections of the individual branches) has a larger current cross section or the same size as the rest of the measuring device, so that the branches do not whether a higher pressure resistance is generated or only slightly higher for the flow of the test gas in the measuring device. The lengths of the various branches, through which the test gas flows, are selected in such a way that volumes of sample gas with a determined volume size are optimally mixed. The mixing takes place in a purely passive way and uses only the pressure difference for the outlet of the measuring device, which induces the flow of the sample gas.
    As an example, the use of the measuring device can be mentioned
    : for breath analysis, in which a single (particularly full) breath is homogenized. Exhalation generates a pressure difference, which induces the flow of the test gas. The average volume of a breath is approximately 500 ml. In branches with three different diameter sizes, with d3: d2: d1 = 3: 2: 1 ratios, the laminar volume current shows different speeds v3 <v2 <v1. Keeping the total mean constant for the individual diameter sizes d1, d2 and d3, because several branches with diameters sizes d1 and d2 are selected, then for all branches with equal diameter, run, approximately, same volume (disregarding friction). At different flow rates than the test gas, the desired volume quantity (eg 500 ml) can now be mixed well by selecting the ra- length. mification. The number of branches makes up at least two. The more branches are used, the more homogeneously the Y 15 test gas can be mixed. A good mixture allows a more accurate and quick measurement of gas components in the test gas. It is important, for example, for highly accurate measurements with pass measurement technique. The diameters of the individual branches are preferably selected in such a way that a second branch is at least 50% larger in diameter, particularly at least 60%, particularly at least 70%, particularly at least 80%, in particular, at least 90%, and especially at least 100%, than a first branch.
    The narrowband emitting laser has a line width of less than 0.2 cm ”in a configuration of the invention, particularly less than 0.05 cm”. In this case, the smaller the line width, the more precisely a given spectral range can be measured. The laser is an example of an infrared quantum cascading laser, which emits light, for example, in the frequency range between 2200 cm ”and 2400 cm”, particularly in the range between 2295 cm ”and 2305 cm” .
    | For the variation of the laser frequency, means are provided for laser tuning, which in one mode apply a periodically modulated voltage with a demodulation frequency to the laser head of the laser, the applied voltage being associated with an increase in temperature short-term and, as a result, a frequency shift. By corresponding voltage modulation, therefore, a repeated increase in temperature and reduction in temperature of the laser can be achieved. The tuning of the laser is, in this case, preferably between 0.5 and 60 cm ”, particularly 1 in”, 2 in ”, 6 in” or 20 cm ”*. The frequency variation determines the spectral range, which is measured. The frequency of modulation determines how often a given spectral range is measured. The modulation frequency is situated in a setting between .- 100 and 500 Hz, particularly between 10 and 100 Hz, particularly, at approximately 50 Hz. The voltage applied to the laser head is in a confi triangular voltage, so that a defined linear frequency spectrum is passed upwards first and then downwards again. Alternatively, saw-tooth tension can be used, for example.
    As already shown, the measurement device according to the invention has a high temporal resolution of individual measurements, which is correlated with a high density of points in the measured spectrum. The detection device, in this case, is formed and adjusted to measure, by spectral range, in which the laser frequency varies, therefore, over a period of the modulation frequency, more than 20 measurement points, preferably more of 100 measuring points, particularly preferably more than 500 measuring points.
    The laser signal that emits the laser is preferably pulsed and in a configuration it has a pulse duration of less than 200 ns, particularly less than 100 ns. The detection device is formed and adjusted, in this case, in a configuration, to carry out an absorption measurement for each pulse of laser light emitted. Each laser pulse therefore leads to an absorbance measurement value.
    ] It may also be foreseen that the detection device will be read with a frequency, which is twice the size of the frequency, with which the laser emits light pulses. The reading therefore takes place with double the number of laser repetitions. This means that only every second reading process refers to a measured pulse of light. The reading processes located between them are not correlated with a measured signal and only reproduce the background signal. The bottom signal is preferably directly deducted. This makes it possible to further increase the measurement signal.
    To increase the measurement accuracy, it is also provided, in a modality variant, that the light emitted by the laser is divided into two partial rays, with a partial ray passing through the measuring chamber: and the other partial ray is detected by a reference detection device. The evaluation unit evaluates the signals of the reference detection device for normalization of the laser signal strength. In this way, oscillations of laser intensity can be calculated, which further increases the accuracy of the measurements made.
    The measuring device according to the invention is set up in a configuration to examine the breathing gas of a human or an animal as a test gas. The measuring device is particularly suitable for determining, with temporal resolution, the ratio of the concentration of isotopes ** CO2 / 2CO> in the human or animal's respiratory gas. There may also be a quantitative measurement of a respiratory gas metabolism parameter in a storm. The measuring device is adjusted, for example, to determine the total amount of ** CO, per breath. In a measurement of several breaths, therefore, this can be accurate to approximately 10 µg. The measuring device is also adjusted to determine, in real time, the concentration of carbon dioxide in the respiratory gas in the range between 0.08% and 8% in passing.
    Another application makes it possible to determine, by means of the measuring device according to the invention, the line width of a
    Õ absorption of the test gas, depending on the gas concentration. Thus, due to the high temporal resolution, the high spectral resolution and the high sensitivity of the absorption measurements carried out, the line width of an observed absorption line can be determined, depending on the concentration of gas. To that end, line widths are measured at defined gas concentrations, previously adjusted. The invention also relates to a process for analyzing a test gas by means of infrared absorption spectroscopy. The process comprises the following steps: - irradiation of a measuring chamber with light, which is emitted by a narrow band laser, whose line width is less than or equal to the width of an infrared absorption line to be measured from a test gas found in the measuring chamber, the frequency of the laser being varied periodically within a defined spectral range and the: 15 laser frequency and its variation are selected in such a way that at least one line infrared absorption rate of the test gas is within the defined spectral range, - detection, with temporal resolution, of the light emitted by the laser and that passes through the measurement chamber, with a single absorption measurement being carried out within 10º s or in a faster way, and - evaluation of the detected signals, referring to a light absorption occurred in the measuring chamber, and the light absorption is determined, with frequency resolution, within the defined spectral range.
    The invention is explained in more detail below, with reference to the figures in the drawings, by means of several examples of modality. They show: figure 1 an example of a measuring device modality, for analyzing a test gas by means of infrared absorption spectroscopy; figure 2 the measurement of a ** CO absorption line; at 2297.10cm ”, using the measurement device of figure 1, and the absorption is represented in dependence of the frequency, in wave numbers, within a measured spectral range; figure 3 the simultaneous measurement of the absorption lines of " CO, and CO>, during two successive breaths, the absorption being represented, on the one hand, against time and, on the other hand, against frequency, in numbers of waves; figure 4 the concentration ratio of ** CO> to " CO, in the measurement range between O DOB and 300 DOB, with the abscissa representing an adjusted concentration ratio of test gases and the ordinate, values measured by the measuring device of figure 1; figure 5 the increase of 13CO, in a test subject, after ingestion of methacetine marked with 13C, depending on time; figure 6 line widths of the Co> absorption lines, depending on the concentration of CO, of the test gas, at an unchanged pressure; Figure 15 shows a schematic representation of a measurement process for determining liver capacity using the measurement device in Figure 1. Figure 1 shows a measuring device 100 for analyzing a test gas by means of absorption spectroscopy. infrared.
    The device 100 comprises a laser 1, a measuring chamber 2, two detectors 61, 2, an antechamber 4, a spirometer 5, a charge intensifier 7 and an evaluation unit 8. Laser 1 is an infrared quantum cascading laser. (QLC), which has a line width below 0.2 in, in particular, a line width of 0.05 in ”. The fundamental frequency of the quantum cascading laser is adjusted through its temperature.
    It is performed on a time scale of approximately 0.05 to 0.5 s using a 92 laser control unit. The laser frequency can be additionally varied periodically within a defined spectral range.
    For this purpose, a voltage is additionally applied to the quantum cascading laser 1, which is subsequently also referred to as “sweep voltage” ", by means of the contact control unit.
    To be 92. The sweep voltage and a sweep current corresponding to it cause a short-term temperature increase during the additional current flow in the laser and thus shift the frequency. The laser parameters are adjusted in such a way that, preferably directly after the end of the current flow, the fundamental frequency is emitted again.
    The sweep tension is continuously increased, for example, by means of a triangular tension or sawtooth tension, and then reduced again, with the result that a continuous frequency variation occurs. Therefore, based on the fundamental frequency, the frequency of laser 1 is varied periodically. The frequency variation is correlated with a laser tuning, which is at least 0.5 cm ”. Examples for. the tuning width is 1, 2, 6, 20 or 60 cm ”. The tuning indicates, in this case, a spectral range, within which the laser frequency is varied. A - At the 15 modulation frequency, with which the laser frequency is varied periodically, it is in the range between 1 and 500 Hz. It defines the frequency with which the observed spectral beech is measured. Next, we start, for example, with a modulation frequency of 50 Hz.
    Laser 1 is a pulsed laser, which emits light signals with a pulse duration of less than 200 ns, particularly 100 ns or even shorter. Thus, the temporal resolution of a measurement is limited to 200 ns or 100 ns. The use of relatively short pulse durations ensures, in that respect, spectral narrow line widths, since in long pulses, a line widening occurs due to an increase in temperature, which is associated with an emission comparatively long laser light.
    The amount of laser, that is, the number of pulses that is emitted per second, is, for example, between 10 and 100 Hz. Next, for example, a 50 Hz laser quantity is assumed.
    Laser 1 is arranged in a closed housing, which prevents contact with the outside air. For this purpose, it is arranged, for example, in a TO3 housing. Cooling with water 96 ensures
    ] laser refrigeration 1. In addition, the control signal for the quantum cascading laser 1 is applied via the laser control unit 92. The measuring chamber 2 has a 21 o -blue input window, by which the laser light enters the measuring chamber 2, and an exit window 22, arranged perpendicularly to the direction of the beam. The light radiated by laser 1 is guided through a lens coated with anti-reflective material 31 over the oblique entrance window 21. In the entry window 21 the light is divided into two partial rays. The transmitted ray passes through the measuring chamber 1, leaves the measuring chamber 2 through the exit window 22 and then, after being focused by another lens 32 coated with anti-reflective material, focuses on a first detector 61. The lenses coated with material - anti-reflective 31, 32, 33, which consist, for example, of ZnSe, sapphire, CaF2 or BaF », are directly connected with laser 1 or the respective: 15 detectors 61.62, so that the measurement structure is only it consists of four components, namely the laser, the two detectors and the measuring chamber. This leads to a simple, robust structure. The laser light passes through the measuring chamber 1 only once, which is formed without mirrors. This further increases the simplicity and the lack of predisposition for defects in the measurement structure. The measuring chamber 2 comprises a temperature control device 23, which is formed, in particular, as a heating device and which is regulated by means of a temperature regulator
    27. The temperature control device 23 ensures a constant temperature inside the measuring chamber, which is, for example, at 35ºC or above. This prevents water vapor, possibly present in the test gas, which permeates the measuring chamber 2, from fogging up the measuring chamber 2. The constant temperature can also be below room temperature. For supplying a test gas to the measuring chamber, it has a first connection 24. The connection 24 is arranged in the housing of the measuring chamber, which consists, for example, of aluminum.
    ! Through connection 24, the test gas 2 is supplied with test gas through an antechamber 4 through a flexible tube 43 or similar.
    A heating device 41 is also associated with the preceding chamber 4, which regulates the temperature of the test gas fed to the measuring chamber through a temperature regulator 42. In this way, the test gas is already heated in the antechamber 4 and its water vapor content is reduced.
    Instead of the heating device 41, a temperature control device 41 could also be used, which, if necessary, could also cool the test gas in the antechamber 4. Furthermore, the measuring chamber 2 has a connection 25 for the test gas leaving the measuring chamber 2. The test gas, in this case, flows through a flexible tube 26 or similar for a spirometer 5,. which determines the volume current, which flows through the measuring chamber 2. After permeating the spirometer 5, the measuring gas exits the measuring device into the environment, and the spirometer 5 may also be disposed at another point in the device measuring
    The test gas flows into the measuring chamber 2 perpendicularly to the direction, in which the laser light passes through the measuring chamber 2. It also flows, perpendicular to the last mentioned direction, again out of the measuring chamber 2. In this case, connections 24, 25 are alternately arranged in the housing of the measuring chamber.
    The entire measuring structure of the measuring device is an open structure, without valves or air valves, which could obstruct the flow of the test gas.
    On the contrary, the test gas can permeate the structure described without hindrance.
    In this chaos, it is expected that the cross section in the supply line 43, in the measurement chamber, as well as in the discharge line 26, is substantially constant, so that at all points a laminar flow is guaranteed and no gas accumulations occur. at certain points.
    On the contrary, the test gas, which enters through the antechamber 4 in the measuring chamber 2, completely displaces the test gas previously existing outside the measuring structure.
    The test gas flows through the antechamber 4 to the measuring chamber 2 and the
    ! measuring chamber 2, by the spirometer, 5 again out of the measuring device.
    Measurements are performed at normal pressure. The measuring chamber 2, the antechamber 4, the supply line 43, the discharge line 26 and the respirometer5 are made in such a way that they are watertight up to an overpressure of up to 20 KPa (200 mbar), compared to normal pressure. In the absence of a pressure difference between gas inlet 24 and gas outlet 25, the test gas can remain unchanged for up to several tens of minutes in the measuring chamber 2.
    The infrared absorption measurements, which are described in more detail below, are carried out at each stage of the gas flow in the measuring chamber 2, particularly also when the test gas. permeates the measuring chamber 2. The measurements carried out take place in real passage. Due to the opening structure of the measuring chamber 2, the 15 tests measuring chamber 2 can be changed at the desired speed. As yet to be explained, the measuring device described is suitable and adjustable to measure the respiratory gas of a human or animal as a test gas. In the case of the use of respiratory gas as a test gas, the respiratory pressure ensures that the new breath displaces the old breath from the measuring chamber, in which case the new breath is measured in real time. With this, the sample of respiratory gas is exchanged in the measuring chamber, with the necessary speed, only by breathing, individually for each patient, and measurements take place in the passage, in real time. The breathing resistance of the measuring device is configured in such a way, in this case, that it is located for the gas flow at less than 6 KPa (60 mbar).
    In the case of detectors 61, 62, these are MCT detectors. These detectors are semiconductor detectors based on mercury (II) cadmium (II) tellurite. Detectors 61, 62 are preferably cooled by the Peltier effect, so it is possible to dispense detectors cooled with liquid nitrogen, despite this high sensitivity. The dispensing of liquid nitrogen for refrigeration expands the area of use of the
    'measuring device, for example, in clinical practice.
    The two detectors 61, 62 are read at almost the same time. In this case, each detector 61, 62 measures the entire spectrum of light emitted by the laser. In this way, errors are avoided by varying the sensitivity from detector to detector.
    The signal read by detectors 61, 62 is first intensified in a power intensifier 7 for each detector and integrated. The intensified signal is then fed, in each case, through an adapter 91 to an evaluation unit 8, which is carried out, for example, by means of a common PC and appropriate software. In this case, the signal from detector 62 serves only to normalize the signal intensity. Thus, the intensity fluctuations in detector 61, which are caused by fluctuations in the intensity of the laser 1, can be corrected by means of the detector signal.
    62. This increases the accuracy of the assessment.
    The evaluation unit 8 also receives signals from the spirometer 5. It can also be provided that the evaluation unit is informed, via a sensor not shown or the temperature regulator 42, 27, the temperature of the test gas and / or the temperature in the measuring chamber 2. A monitor 95 is associated with the evaluation unit 8.
    The evaluation unit 8 generates control signals for the laser control unit 92 with reference to the sweep signal, the laser temperature and the firing frequency. Monitor 95 can graphically represent an evaluation of the absorption measurements made. The evaluation unit 8 may, in addition, be connected to a telecommunications network, for example, to the Internet and / or to a telephone network.
    A mains part 95, which is connected via a transformer 94 to a mains socket, ensures an electrical supply to the various elements of the measuring device.
    As explained, the frequency of laser 1 is periodically varied. The spectral range traversed, in this case, is fixed by the sweep voltage. At a laser quantity of 50 kHz and a sweep voltage of 50 Hz, 1,000 pulses of laser r can be measured per traverse spectral range.
    The observed spectral range is measured, in this case, 50 times per second.
    Measurements can be averaged over a given time, for example, over the length of a breath.
    The detector 61 is formed in such a way that it performs a single absorption change within 10—5 seconds or faster, particularly within 10 seconds or faster.
    A total frequency range, that is, the frequency range of the spectral range defined by the sweep voltage, can be detected in approximately 0.002 to 1 second.
    In the mentioned modality example, the density of points per spectral range (per sweep) is 1,000 points.
    Each laser pulse is detected and transformed into a measurement point.
    Alternatively, the density of points can also be selected in a smaller way, with - approximately 500 points or also only 20 points per spectral range.
    The high density of points when crossing the spectral band to be! 15 measurement, associated with the small spectral line width of laser 1, allows a spectral resolution of less than 0.02 cm ”. This means that the absorption bands of the gas sample can be detected and analyzed very precisely.
    By unfolding or other mathematical processes, the spectral resolution, optionally, can still be further improved.
    Figure 2 shows the measurement of a ** CO ,, absorption line, which is located at a frequency (in wave numbers) of 2,297.19 in ”. The abscissa indicates the change in frequency (due to the sweep voltage) in relation to the fundamental frequency of laser 1. Absorption is indicated in OD (optical density). The dot density is high enough to be able to determine the absorption line very precisely.
    It may be envisaged to adjust the curve.
    An adaptation of the absorption line can take place, for example, with Lorenz curves.
    The data recording takes place, in each case, by means of an analog / digital card, which is provided in the evaluation unit 8 and a microsecond record of one or more data points.
    The resolution, in this case, is better than 12 bits.
    1 At a 50 kHz laser quantity, a 50 Hz sweep current modulation frequency, 50 spectra are measured per second. 1,000 points are measured per spectrum. The reading quantity of detectors 61, 62 is preferably selected in such a way that it is twice the size of the laser quantity. At a laser quantity of 50 kHz, the reading quantity of detectors 61, 62 thus amounts to 100 kHz. This leads to the fact that in each activation process only one detected light signal is read. The measurements that occur between them refer to the background or noise. The reading of detectors 61,62 with the double amount of laser makes it possible to deduce the background immediately, with each measurement of light. This is preferably done in the evaluation unit 8 and further increases the measurement accuracy.
    : With the described measuring device, absorption spectra for a defined spectral range are measured in real time, since: 15 per second a plurality of spectra can be detected. Optionally, in this case, the average over a plurality of spectra can be averaged, which further increases the measurement accuracy. With this, it is possible to detect, in real time, changes in the composition of a test gas.
    To maintain high accuracy, a frequency-stable wing is required. This is achieved by the fact that the temperature control of the laser control unit 92 is additionally controlled by measurement software. In this case, the temperature is readjusted in small steps, so that the same gas-absorbing machine (for example, * CO>) is always located in the same position in the measurement region. In addition, the sweep voltage is also expected to be readjusted, so that the other absorption lines are in the desired position in the measurement region. In this way, measurements can be reproduced optimally and averaged. Signal-to-noise ratio is improved by large media numbers. The measurement software also preferably allows automatic identification of whether the laser power is falling and when laser 1 fails. The corresponding measurement software can be part of the evaluation unit 8 or the laser control unit 92. It can also be envisaged that a quick evaluation of the spectra takes place through the integration of special frequency bands, which must associated with the individual absorption lines. The survey of measurement levels with gas samples, which are known in their composition, allows, in this case, a simple and precise determination of the deviation, without adjusting the data. As the frequency stability is reproducibly adjusted, regions of frequency can be selectively analyzed, from which concentrations are determined with high precision. An adjustment of large amounts of data would possibly slow down the measurement process and is therefore not necessarily necessary. : Due to the high selectivity of measurement, the measurement can take place regardless of test gases, such as oxygen or other anesthetic gases. "With the existing high resolution, influences from any other gas can be separated.
    In the modality example, the measuring device is optimized to perform measurements of hepatic potency, after the administration of metacetin marked with "ºC. ** CO, is proven in the respiratory air. This is described in detail in WO 2007 / 000145 A2, to which reference is made in this regard.
    As shown schematically in figure 7, a patient to be examined wears a respiratory mask, which features an air inlet valve and an air outlet valve. In this way, the inhalation air is separated from the exhalation air. Exhaled air cannot be breathed in again. A flexible plastic tube is connected to the air outlet valve, which guides all respiratory air to the measuring device 100 and which is connected to the antechamber 4. The mask and flexible tubes are also watertight until an overpressure of up to 20 KPa (200 mbar) so as to match the core breathing air by measuring device 100.
    In this case, a measurement software automatically identifies when the mask is not correctly adjusted on the patient's face.
    : loved or has slipped. The measurement software also identifies whether or not the patient is still breathing and, optionally, issues a warning. In addition, the measurement software is expected to identify when the measurement can be completed. Such software can also be integrated into the evaluation unit 8.
    The laser frequency of laser 1 and the spectral range defined by the sweep voltage are then selected in such a way that at least two absorption lines of the sample gas are within the defined spectral range. In the example observed, they are an absorption line of "* Bake a CO absorption line. After the administration of metacetin marked with" ºC, it is dissociated in the liver and can be verified in the respiratory air. The dissociation is correlated with an increase of ** CO, - respiratory air, which leads to a modified ratio of ** CO, to CO> 2. The relationship is determined by the measuring device 100 by means of the measurements: 15 absorption sections and the time course of the same is represented on a monitor 93.
    Figure 3 shows the simultaneous measurement of the CO, and CO »absorption lines over two consecutive breaths. The change in absorption is indicated in OD (optical density). It is registered against time, in seconds, as well as frequency, in wave numbers. You can clearly see the strong variations in absorption and therefore concentration.
    Figure 4 illustrates the precision with which the ratio of * CO / 2CO concentration can be measured. The concentration ratios have been adjusted with exactly characterized test gases and these ratios are verified by means of test measurements. The abscissa shows, in this case, by a DOB value adjusted by test gases. The ordinate shows the measured DOB value, which are determined from the line relations according to figure 3. In this case, 1 DOB designates a modification of the CO ratio, to * CO, by one thousandth above the natural ratio . It is shown that the ratio of ** CO concentration to "CO" can be determined with an accuracy of more than 5 DOB per breath - in the measurement
    'of several breaths in succession.
    The measurement range extends from O DOB to over 1000 DOB in the concentration range from 0.08% to 8% CO ». Over the entire range the ratio is measured with the highest precision.
    Figure 5 shows the determination of hepatic potency after ingestion of metacetin marked with "* C. An increase in * 3CO> of a test subject is shown, which is associated with an increased absorption modification of the ** absorption line. CO ,. Each breath was measured and corresponds to a measurement point (that is, the spectra measured in a breath and the determined ratio of them was averaged for a measurement point.) The increase and maximum of the absorption modification can be determined clearly and quantitatively with precision The diagnostic agent was administered at approximately -3 minutes.
    : 15 Correspondingly, the ratio of other isotopes, elements or molecules can also be determined.
    The measuring device according to the invention allows, in addition to measuring the ratio of certain isotopes, other evaluations as well. For example, the total amount of a metabolism product, for example ** CO, in the breath can be measured. Thus, the volume current, which flows through the measuring chamber 2, is determined with the spirometer 5. As the volume of the measuring chamber 2 is constant and the absorption is determined with temporal resolution, the amount of carbon, which flows through the measuring chamber, can be determined by integration over time. In particular, the concentration can be determined directly from the absorption, since the extinction coefficient for each absorption line is known, as well as the length of the measuring chamber. As the measuring device makes it possible to monitor absorption with temporal resolution, in real time, and also the volume current, with temporal resolution in real time, the total quantity can be determined, in real time, through product integration. volume and concentration over time.
    ! By measuring the concentration of ** CO, and the concentration of 12CO, it can therefore be determined separately for ** CO, and "2CO,>, the amount of carbon dioxide, which is in the measurement chamber. in particular, the total amount of ** CO,> - in the measurement of several breaths in succession - can be determined to approximately 10 µg, exactly per breath.
    Another application determines the detection of changes in the CO absorption lines>, at a variable concentration of CO, in the respiratory air, at an unchanged pressure in the respiratory air. With increasing concentration of gas and / or modifying partial pressure, the line width of the absorption lines is also modified by means of line extension mechanisms, which are themselves known. The line width can be measured at different known concentrations of CO> using the measuring device, compare the absorption lines in figures 2 and 3.
    Figure 6 shows the measured line width, depending on the concentration of * CO, of the respiratory gas in percent. The determined dependency can be assessed for additional error reduction.
    The frequency range for the measurement of "* CO, and" CO, is between 2200 and 2400, in particular, from 2295 to 2305 in ”. In general, a laser 1 is preferably used, which emits light in the frequency range between 2um12um.
    The use of the described measuring device is not limited to the measurement of the CO content of the respiratory air. With the measuring device described, any desired gas sample can be analyzed. In that case, - for example, an isotope ratio of any gases can be determined, in a highly sensitive and very precisely way, in real time. The measuring device according to the invention allows for a quantitative, dynamic and temporal resolution of metabolism parameters, in real time. In that case, load analyzes of a human or animal can also be performed in real time.
    权利要求:
    Claims (15)
    [1]
    1. Measuring device for analyzing a test gas by infrared absorption spectroscopy, which features: - a measuring chamber (2) with the gas to be analyzed, - a laser (1), which is arranged in such a way that in relation to the measuring chamber (2) that the light emitted by the laser passes through the measuring chamber (2), - a detection device (61), which detects the light emitted by the laser (1) and that passes through the measuring chamber measurement (2), and - an evaluation unit (8), which evaluates the signals generated by the detection device (61), with regard to the absorption of light in the measuring chamber (2), and the laser (1) is a laser that emits a narrow band, whose line width is less than or equal to the width of an infrared absorption line to be measured by the test gas and less than 0.2 cm that - the laser (1) is formed and adjusted in such a way that the laser frequency is varied periodically within a defined spectral range, with the frequency of l aser and its variations are selected in such a way that at least one infrared absorption line to be measured for the test gas is within the defined spectral range, and - detection device (61) is formed and adjusted in such a way that it detects, with temporal resolution, the light emitted by the laser (1) and that passes through the measuring chamber (2), in such a way that the light absorption can be determined, with frequency resolution, within of the defined spectral range, characterized by the fact that the detection device (61) is designed and adjusted to perform a single absorption measurement for at least each pulse of light emitted by the laser (1) and within 10º s or faster, and where the measuring device is appropriate and adjustable to measure the breathing gas of a human or animal as a test gas, the respiratory gas being replaced in the measuring chamber only by the person's breathing. or animal and respiratory resistance of the measuring device is less than 6 KPa (60 mbar).
    [2]
    2. Measuring device according to claim 1, characterized by the fact that the laser frequency and its variation are selected in such a way that at least two infrared absorption lines of the test gas are located in the defined spectral range, and where the evaluation unit (8) is designed and adjusted to determine the relationship of two isotopes, elements or molecules of the test gas through the absorption of light that occurred in the two absorption lines.
    [3]
    3. Measuring device according to claim 1 or 2, characterized by the fact that the measuring chamber (2) has an open structure, without valves or ventilation valves, which would obstruct the flow of the test gas to in and out of the measuring chamber (2).
    [4]
    4, Measuring device according to claim 3, characterized by the fact that the measuring device (2) has, between the gas inlet in the measuring device (2) and the gas outlet of the measuring device (2) ), substantially, a constant cross section for the permeation of the test gas.
    [5]
    Measuring device according to claim 3 or 4, characterized by the fact that the measuring device is formed and adjusted in such a way that light detection takes place, with temporal resolution, by the detection device (61 ), during the permeation of the test gas by the measuring chamber (2).
    [6]
    Measuring device according to one of Claims 1 to 5, characterized by a spirometer (5), which detects the volume flow of the test gas, which flows through the measuring chamber (2).
    [7]
    Measuring device according to one of Claims 1 to 6, characterized by an antechamber (4), which is formed to heat or cool the test gas to a certain temperature and reduce the water vapor content of the gas test.
    [8]
    8. Measuring device according to one of the claims
    sections 1 to 7, characterized by the fact that the detection device (61) is formed and adjusted to measure, by spectral range, in which the laser frequency varies, more than 20 measurement points, particularly more than 100 measuring points, particularly more than 500 measuring points.
    [9]
    Measuring device according to one of Claims 1 to 8, characterized in that the laser signal is pulsed, with a pulse duration, preferably less than 200 ns, particularly less than 100 ns ns.
    [10]
    10. Measuring device according to one of claimsla9, characterized by the fact that the detection device (61) is formed and adjusted to be read with a frequency, which is twice the size of the frequency, with the which the laser emits pulses of light.
    [11]
    11. Measuring device according to one of claims 1 to 10, characterized in that the measuring device is configured in such a way that the light emitted by the laser (1) is divided into two partial rays, one of which partial radius passes through the measuring chamber (2) and the other partial radius is detected by a reference detection device (62), and the evaluation unit (8) evaluates the signals of the detection device reference to normalize the signal strength of the
    [12]
    12. Measuring device according to claim 1, characterized by the fact that the measuring device is formed and adjusted to determine the carbon dioxide concentration of the respiratory gas in the range of 0.08% to 8% in permeation, in real time.
    [13]
    13. Measuring device according to one of Claims 1 to 12, characterized in that the measuring device is formed and adjusted to determine the line width of a test gas infrared absorption line, depending on the gas concentration.
    [14]
    14. Process for analyzing a test gas by infrared absorption spectroscopy in a measuring device, as defined in one of claims 1 to 13, with the steps:
    - irradiation of a measuring chamber (2) with light, which is emitted by a narrow band laser (1), whose line width is less than or equal to the width of an infrared absorption line to be measured from one test gas found in the measuring chamber (2) and less than 0.2 cm *, the frequency of the laser being varied periodically within a defined spectral range and the laser frequency and its variation are selected in such a way that at least one infrared absorption line of the test gas is in the defined spectral range, - detection, with temporal resolution, of the light emitted by the laser (1) and passing through the measurement chamber (2), being that a single absorption measurement is performed for at least each pulse of light emitted from the laser and within 10º s or faster, and - evaluation of the detected signals, referring to a light absorption occurred in the measurement chamber (2 ), and the absorption of light is determined, with frequency resolution a, within the defined spectral range, characterized by the fact that the test gas is the respiratory gas of a human or animal, and the respiratory gas is only replaced by the breathing of the human or animal in the measurement chamber , and the respiratory resistance of the measuring device is less than 6 KPa (60 mbar).
    [15]
    15. Process according to claim 14, characterized by the fact that the ratio of two isotopes, elements or molecules of the test gas, which have absorption lines, which are in the defined spectral range, is determined.
    a FIG1 i L - [L so "TA A € VA sn | ta
    E =, 1 = 4:
    - 2HT 1st. the * CO, at 2297.19 cm in the (000) - (001) - transition $. o Branch R with J = 18 E 06 4 2 à o “& o o S 2 & << o2 Fr." the wings to the
    FIG3: E
    EEE 3 LEE HAS ASEEEO
    EEE NESSE 8 SLI ENA a & sr TONI NE $ E 7 AS si e naeaeil
    - 417 o. sm o o
    E 250 o = = q 20 E) o & Ss 150 2 8 100 f and SS so = | Only 100 150 200 250 300 Adjusted DOB value of the gas mixture
    . 57 4th & ”Yeah» FAITH o
    It is' SC 2 º o 2 & o 3 Fá = nº o Breeds 7. Time (minutes)
    - 67 '0.1885 0.1880 & o1t875 0.1870
    FE = 0.1865 2 01880 o 3 0.1855 os mw 01850 - 0.1845 0.1840 Concentration of “CO, in%
    FIG 7: i 3
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    同族专利:
    公开号 | 公开日
    EP2626128B1|2014-11-19|
    EA201200949A1|2013-01-30|
    DE102009055320B4|2011-09-01|
    CA2785489C|2017-08-29|
    PT2515756E|2015-02-24|
    AU2010334907A1|2012-08-16|
    EA022246B1|2015-11-30|
    US9541497B2|2017-01-10|
    DK2515756T3|2015-03-23|
    CN102711605B|2016-01-06|
    PL2515756T3|2015-05-29|
    EP2626128A1|2013-08-14|
    EP2515756A1|2012-10-31|
    CA2785489A1|2011-06-30|
    EP2515756B1|2014-12-10|
    US20110270113A1|2011-11-03|
    AU2010334907B2|2013-08-29|
    ES2531107T3|2015-03-10|
    WO2011076803A1|2011-06-30|
    HK1187301A1|2014-04-04|
    JP5797665B2|2015-10-21|
    JP2013515950A|2013-05-09|
    CN102711605A|2012-10-03|
    DE102009055320A1|2011-06-30|
    HK1175386A1|2013-07-05|
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    法律状态:
    2020-09-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-05| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009055320.7|2009-12-24|
    DE102009055320A|DE102009055320B4|2009-12-24|2009-12-24|Measuring device and method for examining a sample gas by means of infrared absorption spectroscopy|
    PCT/EP2010/070407|WO2011076803A1|2009-12-24|2010-12-21|Measuring device and method for analysing a test gas by means of an infrared absorption spectroscopy|
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