Apparatus and method for detecting at least two trace gases in exhaled air

Abstract

The invention relates to an apparatus (9) for detecting at least two trace gases in exhaled air, containing a first photoacoustic measuring device (1) having a first acoustic resonator (10), at least one first microphone (11) and at least one first light source (12), a device (3) for detecting a resonant frequency of a resonator mode of the first acoustic resonator (10), a device (4) for modulating the first light source (12) with the resonant frequency of the resonator mode, wherein the apparatus (9) also contains a second photoacoustic measuring device (2) having a second acoustic resonator (20), at least one second microphone (21) and at least one second light source (22), wherein the device for modulating the first light source (12) is designed to also modulate the second light source (22) with the resonant frequency of the resonator mode of the first acoustic resonator (10) or a further device (3) is provided for detecting a resonant frequency of a resonator mode of the second acoustic resonator (20) and a further device (4) is provided for modulating the second light source (12) with the resonant frequency of the resonator mode of the second acoustic resonator (20). The invention further relates to a method for determining at least two trace gases in exhaled air.

Description

[0001] Device and method for detecting at least two trace gases in exhaled air

[0002] The invention relates to a device and a method for detecting at least two trace gases in exhaled air, comprising a first photoacoustic measuring device with a first acoustic resonator, at least one microphone, and at least one light source, a device for detecting a resonance frequency of a resonator mode of the first acoustic resonator, and a device for modulating the first light source with the resonance frequency of the resonator mode. The invention further relates to a method for detecting at least two trace gases in exhaled air. Devices and methods of this type can be used for medical diagnostics, for example, for determining the concentration of anesthetics.

[0003] From T. Laurila, T. Sorvajärvi, J. Saarela, J. Toivonen, DW Wheeler, L. Ciaffoni, GAD Ritchie, and CF Kaminski: “Optical Detection of the Anesthetic Agent Propofol in the Gas Phase”, Analytical Chemistry 2011 83 (10) , 3963-3967, it is known to determine the anesthetic propofol by means of a photoacoustic measurement in the exhaled air of a patient during total intravenous anesthesia (TIVA). In this process, the gas to be analyzed is introduced into an acoustic resonator and excited by light of a predetermined wavelength. The wavelength is selected such that it can resonantly excite an optical transition in the target molecule. The excited state of the target molecule decays non-radiatively, resulting in a temperature and pressure fluctuation in the gas.Provided the light source is operated at a resonant frequency of a resonator mode of the acoustic resonator, the photoacoustic signal in the acoustic resonator can be amplified and detected using a microphone.

[0004] This known device has the disadvantage that different trace gases can have overlapping absorption bands, thus reducing the accuracy and / or the detection limit for a given target molecule. Based on the prior art, a possible objective of the invention could be to provide a device and a method for detecting trace gases with higher accuracy.

[0005] According to one aspect, a device for detecting at least two trace gases is disclosed. The trace gases can be present in the exhaled air of a living being, in particular a human being. In some embodiments of the invention, the device can be configured to extract the exhaled air from a ventilator or an anesthesia circuit.

[0006] According to another aspect, a method for detecting at least two trace gases is disclosed. The trace gases can be present in the exhaled air of a living being, in particular a human being. In some embodiments of the invention, the exhaled air can be taken from a ventilator or an anesthesia circuit. In some embodiments, the method according to the second aspect can be carried out with a device according to the first aspect of the present description.

[0007] The device according to one aspect of the present description can comprise a first photoacoustic measuring device. The first photoacoustic measuring device can include a first acoustic resonator, at least one first microphone, and at least one first light source. In some embodiments of the invention, the first acoustic resonator can be a hollow body into which a gas sample to be analyzed is placed.

[0008] The gas sample to be analyzed can be, or contain, the exhaled air of a living being. For the purposes of this description, "exhaled air" is understood to mean a gas that leaves the lungs of the living being. Despite being called "air," it can also be, or contain, a gas that has been provided in a compressed or extremely cold form, for example, an anesthetic gas or medical oxygen. Despite being called "air," its molecular composition may be modified compared to natural ambient air; for example, the oxygen content may be reduced and the carbon dioxide content increased. In addition, the exhaled air may contain trace gases, such as metabolites of the living being.

[0009] The first acoustic resonator can be made of a metal or alloy, a plastic, glass, or ceramic. It can have an elliptical, round, or polygonal shape. The first acoustic resonator can have at least one eigenmode or resonance frequency, which depends on the geometric dimensions and shape of the first resonator and the speed of sound of the gas contained within it. The speed of sound can be influenced by the atomic or molecular composition of the gas and its temperature. The first acoustic resonator can be designed and intended to amplify sound emissions within the gas. For this purpose, it can be provided that the sound emissions are excited at the frequency of at least one eigenmode of the first acoustic resonator.The frequency of at least one eigenmode is also referred to as the resonance frequency of a resonator mode of the first acoustic resonator in the further course of the description.

[0010] To detect trace gases, the trace gas molecules contained in exhaled air can be optically excited. For the purposes of this description, optical excitation is understood to mean the resonant absorption of light, i.e., the photon energy of the light corresponds to the energy of an electronic or vibronic transition in the molecule. For this purpose, light from at least one light source is shone into the gas contained in the first acoustic resonator. Through the absorption of the light, the target molecules to be detected are excited to a higher energy state. The target molecules can release this excitation energy through non-radiative transitions, which can cause a local temperature increase. This can lead to a local increase in pressure.If the first light source is modulated with the resonance frequency of a resonator mode of the first acoustic resonator, an acoustic signal with the resonance frequency is generated and amplified in the first acoustic resonator. The intensity of this acoustic signal is a measure of the concentration of the target molecule. The acoustic signal can be detected with at least one microphone. For the purposes of this description, a non-radiative transition is understood to be the change in the energy level of at least one electron in a molecule in which no photon is emitted. In some embodiments, a non-radiative transition may be selected from the Auger effect, impact ionization, or a vibronic transition in which a molecule changes its vibrational or rotational frequency upon interaction with a photon.

[0011] In some embodiments of the invention, at least one microphone can be a MEMS microphone and / or a condenser microphone. In some embodiments of the invention, a MEMS microphone can have a monolithically integrated amplifier. This can result in a compact and robust design combined with high sensitivity and low susceptibility to interference.

[0012] As explained above, the resonance frequency of the eigenmodes of the first acoustic resonator can change depending on the speed of sound and thus on the molecular composition and temperature. To increase accuracy, some embodiments may therefore include a device for detecting and / or continuously monitoring the resonance frequency of a resonator mode of the first acoustic resonator. This device can detect the resonance frequency continuously or at predefined time intervals and thus control the device for modulating the first light source. For this purpose, the device can excite a higher transverse resonator mode of the first acoustic resonator and detect its frequency. This can increase accuracy because the modulation of the light source is always such that the photoacoustic signals of the target molecules in the first acoustic resonator are amplified.

[0013] In some embodiments of the invention, the device may further include a second photoacoustic measuring device, which contains a second acoustic resonator, at least one second microphone, and at least one second light source. In some embodiments of the invention, the second acoustic resonator may be a hollow body into which a gas sample to be analyzed is placed.

[0014] The second acoustic resonator can be made of a metal or alloy, a plastic, glass, or ceramic. The second acoustic resonator can have an elliptical, round, or polygonal shape. The second acoustic resonator can have at least one natural mode or resonant frequency, which depends on the geometric dimensions and shape of the resonator and the speed of sound of the gas contained within the resonator. In some embodiments of the invention, the shape and / or dimensions of the first acoustic resonator can be identical to the shape and / or dimensions of the second acoustic resonator, so that the natural modes or resonant frequencies of both resonators are identical or nearly identical. For example, the difference can be less than about 5 Hz, less than about 2 Hz, or less than about 1 Hz.The second acoustic resonator can be configured and designed to amplify sound emissions within the gas. For this purpose, it can be provided that the sound emissions are excited at the frequency of at least one eigenmode of the second acoustic resonator. The frequency of at least one eigenmode will also be referred to as the resonance frequency of a resonator mode of the second acoustic resonator in the following description.

[0015] To detect trace gases, the molecules of the trace gas contained in exhaled air can be optically excited. For the purposes of this description, optical excitation is understood to mean the resonant absorption of light, i.e., the photon energy of the light corresponds to the energy of an electronic or vibronic transition in the molecule. For this purpose, light from at least one second light source is shone into the gas contained in the second acoustic resonator. Through the absorption of the light, the target molecules to be detected are excited to a higher energy state. The target molecules can release this excitation energy through non-radiative transitions, thereby causing a temperature increase.If the second light source is modulated with the resonance frequency of a resonator mode of the second acoustic resonator, an acoustic signal at the resonance frequency is generated and amplified in the second acoustic resonator. The intensity of this acoustic signal is a measure of the concentration of the target molecule. The acoustic signal can be detected with at least one second microphone.

[0016] In some embodiments of the invention, at least one second microphone can be a MEMS microphone and / or a condenser microphone. In some embodiments, a MEMS microphone can have a monolithically integrated amplifier. This can result in a compact and robust design with high sensitivity and low susceptibility to interference.

[0017] In some embodiments, the second microphone can be different from the first microphone.

[0018] As explained above, the resonance frequency of the eigenmodes of the second acoustic resonator changes depending on the speed of sound and thus on the molecular composition and temperature. To increase accuracy, some embodiments of the invention may therefore include a device for detecting the resonance frequency of a resonator mode of the second acoustic resonator. This device can continuously detect the resonance frequency or at predefined time intervals and thus control the device for modulating the second light source. This can increase accuracy because the modulation of the light source is always such that the photoacoustic signals of the target molecules in the second acoustic resonator are amplified.In this case, the accuracy of the measurement can be increased because differences in the resonance frequency of the two resonators are taken into account. These differences are caused by varying geometric dimensions and / or temperatures and / or a different composition of the gas contained in each resonator. In some embodiments of the invention, the device for modulating the first light source can also be configured to modulate the second light source with the resonance frequency of the resonator mode of the first acoustic resonator. This is particularly helpful when the geometric dimensions, and thus the resonance frequencies of the resonator modes of the first and second acoustic resonators, are identical. This eliminates the need to determine the resonance frequency of the resonator mode of the second acoustic resonator.

[0019] In some embodiments of the invention, the modulation device can modulate the first and / or second light source by directly modulating the supply current or voltage. Thus, the modulation device can also supply the first and / or second light source with electrical energy. In other embodiments of the invention, the modulation device can control a modulator that interrupts or releases the light beam of the first and / or second light source. The modulator can be selected from a mechanical shutter, a Kerr cell, a Pockels cell, or an LCD element. In yet other embodiments of the invention, the modulation device can effect both direct modulation of the supply current or voltage and the control of a modulator.

[0020] In some embodiments of the invention, the first and / or second acoustic resonator can be adjacent to or connected with at least one hollow body. In some embodiments, two hollow bodies can each be adjacent to opposite ends of the first and second acoustic resonator. The hollow bodies can each provide a buffer volume. This can have the following effects in certain embodiments of the invention, although not all advantages need be realized equally in all embodiments:

[0021] They ensure that the open ends of the resonator reflect the photoacoustically generated sound pressure. In some embodiments, more than 90% of the photoacoustically generated sound pressure can be reflected.

[0022] The inlet and outlet pipes can open into the hollow bodies or into a hollow body. This prevents or reduces interference with the photoacoustic signal caused by flow noise.

[0023] The hollow body(s) can be part of a free-running acoustic oscillator, which enables the detection of the frequency of at least one eigenmode of the acoustic resonator, so that the modulation frequency of the light source can be determined.

[0024] In some embodiments of the invention, the device for detecting and / or continuously tracking the resonant frequency of a resonator mode of the first and / or second acoustic resonator may include a transducer, a microphone, and frequency-selective electronics that amplify the microphone signal and feed it back into the transducer. In some embodiments, the transducer and the microphone are each connected to the hollow body via tubes to form a free-running acoustic oscillator when the device is in operation. The feedback of the frequency-selective electronics and / or the length of the tubes may be selected such that the frequency of the free-running acoustic oscillator is at or close to the first transverse resonant frequency of the hollow body.From this time-varying transverse resonance frequency of the hollow body, the time-varying resonance frequency of the resonator mode of the first and / or second acoustic resonator, and thus the modulation frequency of the first and / or second light source, can be determined. This allows changes in the resonance frequency of the resonator mode caused by changes in the composition of the exhaled air and / or temperature to be detected and taken into account, thereby increasing the accuracy of the measurement.

[0025] In some embodiments of the invention, the first and / or second light source can be selected from a light-emitting diode (LED), a superluminescent diode (SLED), and / or a semiconductor laser. In some embodiments, the first and second light sources can have different wavelengths or frequencies. This makes it possible to detect a first trace gas in the first photoacoustic measuring device and a second trace gas in the second photoacoustic measuring device. The first trace gas can be different from the second. In some embodiments, the optical absorption bands of the first and second trace gases can overlap, so that the sum of both trace gases is detected in the first photoacoustic measuring device, whereas only one of the two trace gases is detected in the second photoacoustic measuring device.The concentration of the other trace gas can thus be determined from the difference between the two measured values. As a result, the concentration of two trace gases in exhaled air can be reliably determined by two independent differential absorption measurements.

[0026] In some embodiments of the invention, the first and / or second light source may be provided with optics designed and intended to collect and / or collimate the light emitted from the light source and / or to focus it into a target volume within the first or second acoustic resonator. This may increase the signal intensity and / or the signal-to-noise ratio. In some embodiments, the optics may contain or consist of a lens. In other embodiments, the optics may contain or consist of a plurality of lenses or a lens system. In some embodiments, the optics may contain or consist of a collimator and / or an aperture.

[0027] In some embodiments of the invention, the first and second acoustic resonators can be arranged one after the other in the direction of exhaled airflow. The exhaled air thus first flows through the first acoustic resonator and subsequently through the second. The photoacoustic measurement is therefore performed sequentially on a predetermined quantity of gas using both photoacoustic measuring devices in order to determine different trace gases in a single gas sample.

[0028] In some embodiments of the invention, an acoustic band-stop filter can be arranged between the first and second acoustic resonators. This allows the gas to flow between them without causing acoustic coupling between the two resonators. This at least reduces the crosstalk of the photoacoustic signal from one resonator into the microphone of the other. The acoustic band-stop filter is an acoustic filter that attenuates a specific frequency band and, in the limiting case, blocks it entirely. The band-stop filter can be tuned to the resonant frequency of the resonator mode.

[0029] In some embodiments of the invention, the acoustic bandstop filter can be, or include, a common partition between the first and second acoustic resonators. The partition can have a bore that allows the supplied gas to flow from the first resonator into the second. In some embodiments, the bore can have a diameter of approximately 0.1 mm to approximately 1 mm or approximately 0.5 mm to approximately 2 mm. This allows the gas to flow without acoustically coupling the two resonators. This can at least reduce the crosstalk of the photoacoustic signal from one resonator into the microphone of the other resonator.

[0030] In some embodiments of the invention, the acoustic bandstop filter may contain or consist of at least one X / 4 tube through which the exhaled air flows between the first acoustic resonator and the second acoustic resonator during operation of the device. For the purposes of this description, an X / 4 tube means a tube whose length is 1 / 4 of the wavelength of the sound frequency to be attenuated and the associated end correction (mouth correction).

[0031] In some embodiments of the invention, the first acoustic resonator and the second acoustic resonator can be arranged parallel to each other in the direction of flow of exhaled air.

[0032] In some embodiments of the invention, an acoustic bandstop filter can be arranged at the input of the first acoustic resonator and at the input of the second acoustic resonator.

[0033] In some embodiments of the invention, the exhaled air can flow through an X / 4 tube at the inlet of the first acoustic resonator and at the inlet of the second acoustic resonator when the device is in operation.

[0034] In some embodiments of the invention, the first light source can be configured to emit light with a wavelength of approximately 270 nm to approximately 300 nm. In other embodiments of the invention, the first light source can be configured to emit light with a wavelength of approximately 270 nm to approximately 280 nm. This allows the first photoacoustic measuring device to be configured to detect the trace gases acetone and propofol.

[0035] In some embodiments of the invention, the second light source can be configured to emit light with a wavelength of approximately 290 nm to approximately 310 nm. This allows the second photoacoustic measuring device to be configured to detect the trace gas acetone.

[0036] In some embodiments of the invention, the first photoacoustic measuring device can have a plurality of first light sources. The individual light sources of a plurality of first light sources can be configured and designed to emit different wavelengths. In some embodiments of the invention, the second photoacoustic measuring device can have a plurality of second light sources. The individual light sources of a plurality of second light sources can be configured and designed to emit light of different wavelengths. This allows different trace gases to be detected in each photoacoustic measuring device, or the selectivity can be increased by exciting multiple absorption lines of a target molecule by different light sources.

[0037] In some embodiments of the invention, the first light sources of the first photoacoustic measuring device can be configured to emit light at 308 nm and 295 nm. These wavelengths are absorbed by propofol and acetone and can thus lead to the formation of a photoacoustic signal in gases containing acetone and propofol.

[0038] In some embodiments of the invention, the second light sources of the second photoacoustic measuring device can be configured to emit light at 295 nm and 275 nm. These wavelengths are absorbed by acetone and can therefore lead to the formation of a photoacoustic signal in acetone-containing gases.

[0039] In some embodiments of the invention, the light sources can emit three different wavelengths, with a first wavelength of approximately 275 nm, corresponding approximately to the optical absorption maximum of propofol and acetone; a second wavelength of approximately 295 nm, which is weakly absorbed by propofol and moderately absorbed by acetone; and a third wavelength of approximately 308 nm, which is not absorbed by propofol and moderately absorbed by acetone. This allows for effective determination of the propofol concentration, even if the exhaled air also contains acetone. Similarly, other trace gases with partially overlapping absorption bands can be detected if the wavelengths of the light sources are appropriately matched.

[0040] In some embodiments of the invention, the device can further include at least one feed pump, which is configured to pump exhaled air or another gas to be analyzed through a supply line through the first and second acoustic resonators. This enables a continuous gas exchange, which allows for continuous measurement of the trace gases.

[0041] In some embodiments of the invention, a pressure measuring device and at least one throttle valve may be present in the discharge line. In other embodiments of the invention, a pressure measuring device and at least one throttle valve may be present in the supply line. The pressure measuring device may be configured and designed to detect a pressure drop across the throttle valve. From this, the flow rate through the supply line and the photoacoustic measuring devices can be determined from the pressure drop. The supply line is arranged upstream of the photoacoustic measuring devices in the direction of flow. The discharge line is arranged downstream of the photoacoustic measuring devices in the direction of flow.

[0042] In some embodiments of the invention, an additional throttle valve may be present in the supply line or the discharge line to control or regulate the flow. In some embodiments of the invention, the flow may be between approximately 30 cm 3 -min - 1 and about 120 cm 3 -min - 1 amount to .

[0043] In some embodiments of the invention, the device further includes at least one heating element with which the first acoustic resonator and / or the second acoustic resonator and / or the supply line can be heated. This reduces the adsorption of the trace gases on the inner surfaces of the supply line and / or the acoustic resonators, so that the measurement accuracy and / or the response of the device can be increased. In some embodiments of the invention, the heating element can be configured or designed to bring at least a partial surface of an acoustic resonator and / or the supply line to a temperature of approximately 80° to approximately 180°. In other embodiments of the invention, the heating element can be designed to bring at least a partial surface of an acoustic resonator and / or a partial surface of the supply line to a temperature of approximately 100° to approximately 120°.This reliably prevents the undesired adsorption of trace gases on the inner surfaces of the device. In some embodiments of the invention, the heating device can be configured to regulate a preset temperature with an accuracy of approximately ±0.3 °C.

[0044] In some embodiments of the invention, at least a partial surface of the inner surfaces of the first acoustic resonator and / or at least a partial surface of the inner surfaces of the second acoustic resonator and / or at least a partial surface of the inner surfaces of the supply line can be provided with a coating. Such a coating can prevent or reduce the adsorption of the trace gases to be detected, either as an alternative or in addition to the heating device.

[0045] In some embodiments of the invention, such a coating can contain or consist of silicon and / or silicon oxide. Such coatings are easy to produce and form nearly inert surfaces for a wide variety of trace gases.

[0046] In some embodiments of the invention, a first connecting tube may be arranged between the first microphone and the first acoustic resonator. In some embodiments, a second connecting tube may be arranged between the second microphone and the second acoustic resonator. The length of the connecting tube(s) may, in some embodiments, be selected such that the effects of the acoustic impedances of the microphones on the resonant frequencies of the resonators are compensated for or at least reduced. The connecting tube(s) may, in some embodiments of the invention, contain or consist of glass, plastic, or ceramic. In some embodiments of the invention, the connecting tube may contain or consist of polytetrafluoroethylene. A connecting tube may have an inner diameter of approximately 1 mm to approximately 3 mm or of approximately 1.5 mm.Such a connecting tube can have the effect of keeping the first and / or second microphone at a lower temperature than the first and / or second acoustic resonator, respectively. This can prevent or delay damage to the first and / or second microphone due to overheating. The invention will be explained in more detail below with reference to figures, without limiting the general concept of the invention. [Figures shown here are not provided in the original text.]

[0047] Figure 1 shows the general structure of the device.

[0048] Figure 2 shows a first embodiment of the photoacoustic measuring device as a block diagram.

[0049] Figure 3 shows an enlarged section of Fig. 2.

[0050] Figure 4 shows a cross-sectional embodiment of a photoacoustic resonator.

[0051] Figure 5 shows a second embodiment of the photoacoustic measuring device.

[0052] Figure 6 shows a third embodiment of the photoacoustic measuring device

[0053] Figure 7 shows another embodiment of an acoustic band-stop filter.

[0054] Figure 8 shows the modulation frequency of the first light source and the photoacoustic signal of the first microphone as a function of the gas composition.

[0055] Figure 9 shows a flowchart of the proposed measurement procedure.

[0056] Figure 1 shows the general structure of the measuring device described here. The measuring device comprises the apparatus 9, which is explained in more detail with reference to Figure 2, for detecting at least two trace gases in exhaled air. In some embodiments of the invention, the exhaled air can originate from a living being, in particular from a ventilated human patient. In this case, the exhaled air can be taken from the outlet of a ventilator or an anesthesia circuit and fed to the apparatus 9.

[0057] Furthermore, the measuring device includes an electrical power supply 91, which supplies the device 9 with electrical energy. The measured values ​​generated by the device 9 can be digitized by means of an A / D converter 92 and fed to an electronic data processing system 93. The electronic data processing system 93 can store or visualize the measured values ​​or make them available for controlling or regulating other devices. In addition, the electronic data processing system 93 can generate control signals that control the device 9 for detecting trace gases and perform specific measurements at certain time intervals.

[0058] Figure 2 illustrates a first embodiment of the device 9 for detecting at least two trace gases in exhaled air 55. The device 9 comprises at least one first photoacoustic measuring device 1 and at least one second photoacoustic measuring device 2. The first photoacoustic measuring device 1 includes a first acoustic resonator 10, at least one first microphone 11, and at least one first light source 12. In the illustrated embodiment, two first light sources 12 are shown, which emit light of different wavelengths.

[0059] The second photoacoustic measuring device 2 has a second acoustic resonator 20. Sound signals in the second acoustic resonator can be detected with at least one second microphone 21. Furthermore, the second photoacoustic measuring device also contains at least one second light source 22. In the illustrated embodiment, two second light sources 22 are present, which emit light of different wavelengths. The acoustic resonators 10, 20 essentially contain a cavity through which the exhaled air 55 to be analyzed flows. In the illustrated embodiment, the first and second acoustic resonators 10, 20 are arranged one behind the other in the direction of flow of the exhaled air 55. Thus, the first acoustic resonator 10 and the second acoustic resonator 20 are sequentially flowed through by the exhaled air 55.In some embodiments of the invention, the first and second acoustic resonators can have identical geometric dimensions, so that they exhibit the same eigenmodes and the same resonant frequencies. This can simplify the modulation of the first and second light sources, because they can be modulated at the same frequency.

[0060] The flow of exhaled air 55 through the supply line 51 and the first and second acoustic resonators 10 and 20 is maintained by a pump 50. The pump 50 can be a micropump. The pump 50 can be switched on and off via a control line 56 in order to adjust the flow of exhaled air 55 to the respective measurement. The flow can be adjusted between approximately 30 cm 3 / see and about 150 cm 3 / see or between about 50 cm 3 / see and about 100 cm 3 / see amount .

[0061] The supply line 51 and the inner surfaces of the acoustic resonators 10 and 20 can be coated with a layer that reduces or prevents the adhesion of the trace gases to be detected. Such a layer can contain or consist of silicon and / or silicon oxide. Furthermore, the adsorption of the trace gases can be reduced if the supply line 51 and / or the first acoustic resonator 10 and / or the second acoustic resonator 20 are heated to an elevated temperature, for example, approximately 80° to approximately 180° or approximately 100° to approximately 120°. A heating device 6 can be provided for this purpose, which, for example, enables an elevated temperature via an electric resistance heater. In addition, the heating device 6 can include a control or regulating device that maintains the temperature at a constant value.For this purpose, the heating device 6 can have line connections 62 and 63, which are connected to the respective components to be heated. The supply line 51 and / or the first acoustic resonator 10 and / or the second acoustic resonator 20 can optionally be connected to a temperature sensor, which records the actual temperature value and transmits it to the heating device 6. Optionally, the heating device 6 can have a further line 61, which can be configured to transmit setpoint or actual values ​​to the electronic data processing system 93.

[0062] As can be seen from Figure 2, the first photoacoustic measuring device 1 in the illustrated embodiment has two first light sources 12, each emitting light of different wavelengths. For example, one light source can emit light with a wavelength of 308 nm and the other light source can emit light with 295 nm. Thus, the first photoacoustic measuring device can be sensitive to acetone but insensitive to propofol.

[0063] The absorption of light leads to a pressure fluctuation in the acoustic resonator, which can be detected as a sound signal by at least one microphone 11. The microphone 11 can, for example, be a MEMS microphone.

[0064] In the illustrated embodiment, the second photoacoustic measuring device 2 has two second light sources 22. One light source is configured and designed to emit light with a wavelength of 295 nm. The other light source is configured and designed to emit light with a wavelength of 275 nm. Thus, the second photoacoustic measuring device 2 is sensitive to acetone and propofol. The concentration of propofol can then be determined from the difference between the measurement signals of the first photoacoustic measuring device 1 and the second photoacoustic measuring device 2.

[0065] The light from at least one second light source 22 also produces a photoacoustic signal, which can be detected with a second microphone 21. The second microphone 21 can also be a MEMS microphone. The signals from the first and second microphones 11 and 21 can be fed to a measuring amplifier 7 via its inputs 71. The measuring amplifier 7 can amplify the signals analogously and output them via its outputs 72. The outputs 72 can be connected to the A / D converter 92 and supply the digitized measured values ​​to the electronic data processing system 93.

[0066] The first and second light sources 12, 22 are operated via a device 4 for modulation with the resonant frequency of a resonator mode. Through resonant excitation, the acoustic resonators can amplify the photoacoustic signal so that it can be detected with an improved signal-to-noise ratio by the first and second microphones 11, 21.

[0067] Since the frequency of a resonator mode used for measurement in the acoustic resonators 10, 20 changes with temperature and gas composition, the device 9 further includes a device 3 for detecting a resonator mode's resonance frequency. The frequency detected in this way is made available to the data processing device 93 via a first output 31. Furthermore, the first input 31 is connected to the input 41 of the device 4 for modulating the light sources. The modulation signals supplied by the device 4 modulate the light sources via lines 42 and 43. A modulation signal is also sent via line 44 to the A / D converters 92, where it serves as a phase reference.

[0068] The device 3 for detecting a resonant frequency can optionally have a second output 32, which provides a clock signal for the A / D converter 92. The frequency at the second output 32 can be a multiple of the frequency at output 31, so that the operating frequency of the A / D converter is a multiple of the modulation frequency of the first and second light sources. This means that during digitization, the same number of digital data points are always generated from one period of the microphone signal, regardless of how the resonant frequency changes. This method makes the evaluation of the measurement data simpler and more accurate. The frequency multiplier can be adjusted in some embodiments of invention 2. n In some embodiments, 1 < n < 8 may be chosen. In other embodiments, 3 < n < 6 may be chosen.

[0069] The acoustic resonators, light sources, and microphones are shown again in enlarged detail in Figure 3. Figure 3 also shows a different section through resonators 10 and 20. The section is approximately orthogonal to the preceding Figure 2. Identical components of the invention are labeled with the same reference numerals, so the following description is limited to the essential differences.

[0070] As can be seen in Figure 3, the first and second microphones 11, 21 are connected to their respective acoustic resonators 10, 20 via first and second connecting tubes 13, 23. This feature allows the first and second microphones 11, 21 to be kept at a lower temperature than their respective associated acoustic resonators 10, 20. This prevents premature aging or damage to the microphones. Figure 3 further shows that a throttle valve 53 and a pressure measuring device 52 are present in the discharge line 54. The throttle valve 53 can cause a pressure drop of approximately 20 hPa to approximately 40 hPa. The pressure sensor 52 can have a measuring range of less than 100 hPa. In some embodiments of the invention, the pressure sensor 52 can be configured to detect a pressure loss via the throttle valve 53.The flow rate through the acoustic resonators can thus be determined with high accuracy from the pressure loss. In other embodiments of the invention, the throttle valve 53 and the pressure sensor 52 can also be arranged in the supply line 51 instead of in the discharge line 54.

[0071] Figure 3 further shows that the acoustic resonators 10 and 20 have a common partition, which has at least one bore 15 that allows the supplied gas to flow from the first resonator 10 into the second resonator 20. In some embodiments of the invention, the bore 15 can have a diameter of approximately 0.1 mm to approximately 1 mm or from approximately 0.5 mm to approximately 2 mm. In some embodiments of the invention, the at least one bore 15 forms a bandpass filter. This is designed and intended to allow the gas to flow through and to prevent or reduce acoustic coupling between the two resonators 10 and 20. This can at least reduce the crosstalk of the photoacoustic signal from one resonator into the microphone of the other resonator.Acoustic band-stop filters are therefore acoustic filters that attenuate a specific frequency band and, in extreme cases, block it entirely. These band-stop filters can be tuned to the resonant frequency of the resonator mode used for photoacoustic measurements.

[0072] Figure 4 shows a cross-sectional embodiment of a photoacoustic resonator 10. In the embodiment shown in Figure 4, the photoacoustic resonator 10 is bounded by a wall 110. The wall can contain or consist of a metal, an alloy, a plastic, or glass. The inner surface can be provided with an optional coating.

[0073] The opposing side surfaces of the photoacoustic resonator 10 are open, i.e., essentially material-free, and border two hollow bodies 101 and 102. The open side surfaces allow for gas exchange between the hollow bodies 101 and 102 and the photoacoustic resonator 10. The hollow bodies each constitute a buffer volume. In certain embodiments of the invention, this can have the following effects, although not all advantages need be realized equally in all embodiments:

[0074] The hollow bodies 101, 102 ensure that the open side surfaces of the resonator reflect the photoacoustically generated sound pressure. In some embodiments, more than 90% of the photoacoustically generated sound pressure can be reflected.

[0075] The supply and discharge lines 51 and 54 can open into the hollow bodies 101 and 102. The bore 15 described above, which allows the supplied gas to flow from the first resonator 10 into the second resonator 20 and acts as an acoustic bandstop filter, can also be located in adjacent hollow bodies 101 and 102. This prevents or reduces interference with the photoacoustic signal caused by flow noise.

[0076] The hollow body(s) 101, 102 can be part of a free-running acoustic oscillator, which enables the detection of the frequency of at least one eigenmode of the acoustic resonator, so that the modulation frequency of the light source can be determined.

[0077] Since the hollow bodies 101, 102 have a larger cross-section than the photoacoustic resonator 10, recesses 111 are formed into which a microphone (not shown) can be positioned. The sides of the hollow bodies 101, 102 facing away from the photoacoustic resonator 10 each have a window 121, 122 through which the light from the light sources 12, 22 can be coupled into the photoacoustic resonator 10. The second photoacoustic resonator 20 can have an identical structure. Thus, gas to be analyzed can enter the first hollow body 101 through the supply line 51 and from there flow through the photoacoustic resonator 10 into the second hollow body 102.

[0078] From there, the gas flows through bore 15 (not visible in Fig. 4) into a hollow body of the second measuring device. It then flows through the second photoacoustic resonator 20 into the other hollow body of the second measuring device and through the discharge line 54 to the pump 50.

[0079] The operation of device 3 for detecting the modulation frequency is explained again using an example in Figure 8. The modulation frequency is shown in curve A on the right ordinate, and the photoacoustic signal in curve B on the left ordinate. The measured values ​​are plotted against time, whereby the gas composition within the acoustic resonators changes over time.

[0080] During the time range of 0 to 34 minutes and from 58 to 67 minutes, room air is supplied with a volume flow of 100 cm³. 3 / min drawn in. As curve A shows, this results in an essentially constant frequency of the resonator mode. The small jumps shown represent the digital resolution of the frequency tracking of approximately 1.7 Hz.

[0081] Between 34 and 58 minutes (labeled ti and t2 on the abscissa), room air is heated to 90 cm³. 3 / min and a gas mixture with 10 cm 3 The gas mixture is drawn in at a rate of [percentage] per minute and passed through the acoustic resonator. The gas mixture contains 500 ppm acetone in nitrogen. As shown in Figure 8, the frequency tracking captures the resonant frequency of the resonator mode, which changes by approximately 5 Hz. The photoacoustic signal in curve B can still be captured by adjusting the modulation frequency.

[0082] A second embodiment of the device 9 for detecting at least two trace gases in exhaled air 55 is explained in more detail with reference to Figure 5. Identical components of the invention are designated with the same reference numerals, so that the description is limited to the essential differences. Furthermore, not all components are shown in Figure 5. These may be arranged in the same or a similar manner as described in connection with Figure 2.

[0083] The device 9 comprises at least one first photoacoustic resonator 10 and at least one second photoacoustic resonator 20. The opposing sides of the photoacoustic resonator 10 are open, i.e., essentially free of material, and adjoin two hollow bodies 101 and 102. The open sides allow gas exchange between the hollow bodies 101 and 102 and the photoacoustic resonator 10. Each hollow body represents a buffer volume, as described in connection with Fig. 4. The sides of the hollow bodies 101, 102 facing away from the photoacoustic resonator 10 each have a window 121, 122 through which the light 120 of the light sources not shown can be coupled into the photoacoustic resonator 10.

[0084] Similarly, the opposing side surfaces of the photoacoustic resonator 20 are open, i.e., essentially material-free, and adjoin two hollow bodies 201 and 202. The open side surfaces allow for gas exchange between the hollow bodies 201 and 202 and the photoacoustic resonator 20. The hollow bodies 201 and 202 each also constitute a buffer volume, as described in connection with Fig. 4. The sides of the hollow bodies 201 and 202 facing away from the photoacoustic resonator 20 each have a window 221 and 222, through which the light 220 from the light sources (not shown) can be coupled into the photoacoustic resonator 20.

[0085] During operation of the device, the gas to be analyzed flows through the supply line 51 into the first hollow body 101 and from there through the photoacoustic resonator 10 into the second hollow body 102. From there, the gas flows via the X / 4 tube 85 into the hollow body 202 of the second measuring device 2. It then flows through the second photoacoustic resonator 20 into the other hollow body 201 of the second measuring device 2 and through the discharge line 54 to the pump (not shown).

[0086] Acoustic bandstop filters 8 are located between the supply line 51 and the first hollow body 101 of the first measuring device, and between the first hollow body 201 of the second measuring device and the discharge line 54. These filters each contain a buffer volume 80 and a subsequent X / 4 tube 85, through which the gas flows sequentially. The bandstop filters 8 are designed and intended to allow the gas to flow over them while simultaneously preventing acoustic coupling of the two resonators 10, 20 with the pump or other sources of acoustic interference.

[0087] The X / 4 tube 85, arranged between the two resonators 10 and 20, together with the hollow bodies 102 and 202, forms a bandstop filter 8. This filter is designed and intended to allow gas to flow through without causing acoustic coupling between the two resonators 10 and 20. This reduces the crosstalk of the photoacoustic signal from one resonator into the microphone of the other. The acoustic bandstop filters are therefore acoustic filters that attenuate a specific frequency band and, in extreme cases, block it entirely. The bandstop filters can be tuned to the resonant frequency of the resonator mode used for the photoacoustic measurement.

[0088] A third embodiment of the device 9 for detecting at least two trace gases in exhaled air 55 is explained in more detail with reference to Figure 6. Identical components of the invention are designated with the same reference numerals, so that the description is limited to the essential differences. Furthermore, not all components are shown in Figure 5. These may be arranged in the same or a similar manner as described in connection with Figure 2.

[0089] As can be seen in Fig. 6, the photoacoustic resonators 10 and 20 are arranged in parallel. During operation of the device, gas to be analyzed flows through the supply line 51, which branches before the photoacoustic resonators 10 and 20, into the first hollow bodies 101 and 201, and from there through the photoacoustic resonators 10 and 20 into the second hollow bodies 102 and 202. From there, the gas flows through the discharge line 54 to the pump (not shown).

[0090] Between the supply line 51 and the first hollow bodies 101 and 201, and between the second hollow bodies 102 and 202 and the discharge line 54, there are acoustic bandstop filters 8. These each contain a buffer volume 80 and two adjoining X / 4 tubes 85, which divide the gas flow. The bandstop filters 8 are designed and intended to allow gas to flow over them while simultaneously preventing acoustic coupling between the two resonators 10, 20 and with the pump or other sources of acoustic interference.

[0091] Figure 7 shows another embodiment of an acoustic bandstop filter 8. The bandstop filters 8 according to Figures 5 and 6 each contain a buffer volume 80 and an X / 4 tube 85. In contrast, the bandstop filter 8 according to Figure 7 contains a plurality of X / 4 tubes 85, each separated from the others by a buffer volume 80. This allows the slope of the bandstop filter 8 to increase, which can result in less crosstalk.

[0092] Figure 7 shows four X / 4 tubes 85, each separated from the others by a buffer volume 80. In other embodiments, the number of X / 4 tubes 85 can be greater or lesser and may be between 2 and 10 or between 3 and 6.

[0093] The operation of the proposed device is further explained with reference to Figure 9. The left side of the figure shows a free-running acoustic oscillator, which contains at least one of the hollow bodies 101, 201, 102, and 202, a microphone, an analog amplifier, and a loudspeaker. The free-running acoustic oscillator is operated at a frequency that differs significantly from the resonant frequency of the first and second acoustic resonators. For example, the frequency can be approximately two to four times higher. The resulting frequency of the free-running acoustic oscillator is a measure of the change in the speed of sound and thus also a measure of the change in the frequency of the resonator mode, which is used for the photoacoustic measurement.

[0094] The resulting frequency can be measured and subsequently fed to device 4 for modulating the light sources. The modulated light sources then excite the photoacoustic signal, which is captured, amplified, and digitized by the first and second microphones.

[0095] Naturally, the invention is not limited to the embodiments shown. The preceding description is therefore not to be considered limiting, but rather explanatory. The following claims are to be understood as meaning that a named feature is present in at least one embodiment of the invention. This does not preclude the presence of further features. The following claims are not to be understood as meaning that a named feature must be present in every embodiment of the invention. Insofar as the claims and the preceding description define "first" and "second" embodiments, this designation serves to distinguish between two similar embodiments without establishing a hierarchy.

Claims

Claims 1. Device (9) for detecting at least two trace gases in exhaled air (55), comprising a first photoacoustic measuring device (1) with a first acoustic resonator (10), at least one first microphone (11), and at least one first light source (12), which is configured to be permeated by the exhaled air (55); a device (3) for detecting a resonance frequency of a resonator mode of the first acoustic resonator (10); a device (4) for modulating the first light source (12) with the resonance frequency of the resonator mode; characterized in that the device (9) further comprises a second photoacoustic measuring device (2), comprising a second acoustic resonator (20), at least one second microphone (21), and at least one second light source (22), wherein the second photoacoustic measuring device (2) is configured to be permeated by the exhaled air (55) in parallel or sequentially;wherein the device (4) for modulating the first light source (12) is configured to also modulate the second light source (22) with the resonance frequency of the resonator mode of the first acoustic resonator (10), or a further device (3) for detecting a resonance frequency of a resonator mode of the second acoustic resonator (20) and a further device (4) for modulating the second light source (12) with the resonance frequency of the resonator mode of the second acoustic resonator (20) are provided.

2. Device according to claim 1, characterized in that the first acoustic resonator (10) and the second acoustic resonator (20) are arranged one behind the other in the direction of flow of the exhaled air (55).

3. Device according to claim 2, characterized in that an acoustic bandstop filter (8) is arranged between the first acoustic resonator (10) and the second acoustic resonator (20) and / or that the exhaled air (55) flows through at least one Ä. / 4 tube (85) between the first acoustic resonator (10) and the second acoustic resonator (20) during operation of the device.

4. Device according to claim 1, characterized in that the first acoustic resonator (10) and the second acoustic resonator (20) are arranged parallel to each other in the direction of flow of the exhaled air (55).

5. Device according to claim 4, characterized in that an acoustic bandstop filter (8) is arranged at the inlet of the first acoustic resonator (10) and at the inlet of the second acoustic resonator (20) and / or that the exhaled air (55) flows through an Ä. / 4 tube (85) at the inlet and / or at the outlet of the first acoustic resonator (10) and at the inlet and / or at the outlet of the second acoustic resonator (20) when the device is in operation.

6. Device according to one of claims 1 to 5, characterized in that the first light source (12) is configured to emit light with a wavelength of about 270 nm to about 300 nm and / or that the first light source (12) is configured to emit light with a wavelength of about 270 nm to about 280 nm and / or that the second light source (22) is configured to to emit light with a wavelength of approximately 290 nm to approximately 310 nm.

7. Device according to one of claims 1 to 6, characterized in that the first photoacoustic measuring device (1) and / or the second photoacoustic measuring device (2) each have a plurality of first and second light sources (12, 22) and / or that the first light sources (12) are configured to emit light at 308 nm and 295 nm and / or that the second light sources (22) are configured to emit light at 295 nm and 275 nm.

8. Device according to one of claims 1 to 7, further comprising at least one feed pump (50) which is configured to convey the exhaled air through a supply line (51) through the first and second acoustic resonator (10, 20).

9. Device according to claim 8, further comprising a pressure measuring device (52) and at least one throttle valve (53) in the discharge line (51) .

10. Device according to one of claims 1 to 9, further comprising at least one heating device (6) with which the first acoustic resonator (10) and / or the second acoustic resonator (20) and / or the supply line (51) can be brought to a temperature of about 80°C to about 180°C or of about 100°C to about 120°C.

11. Device according to one of claims 1 to 10, characterized in that at least a partial surface of the inner surfaces of the first acoustic resonator (10) and / or the second acoustic resonator (20) and / or the supply line (51) are provided with a coating or that at least a partial surface of the inner surfaces of the first acoustic resonator (10) and / or the second acoustic resonator (20) and / or the supply line (51) are coated with a coating containing or consisting of silicon and / or silicon oxide.

12. Device according to one of claims 1 to 11, characterized in that a first connecting tube (13) is arranged between the first microphone (11) and the first acoustic resonator (10) and / or that a second connecting tube (23) is arranged between the second microphone (21) and the second acoustic resonator (20).

13. Device according to claim 12, characterized in that the first and / or second connecting tube (13, 23) contains or consists of polytetrafluoroethylene.

14. Method for determining at least two trace gases in exhaled air, comprising the following steps Supplying a partial stream of exhaled air to a first photoacoustic measuring device (1) with a first acoustic resonator (10) , at least a first microphone (11) and at least a first light source (12) , Detecting a resonance frequency of a resonator mode of the first acoustic resonator (10) , Modulating the first light source (12) with the resonance frequency of the resonator mode of the first acoustic resonator (10) , Capturing the photoacoustic signal in the first acoustic resonator (10) with the at least one first microphone (11), characterized in that the partial flow of exhaled air is further supplied to a second photoacoustic measuring device (2), which contains a second acoustic resonator (20), at least one second microphone (21) and at least one second light source (22), wherein the second photoacoustic measuring device (2) is supplied with exhaled air (55) in parallel or sequentially. are; wherein the second light source (22) is also modulated with the resonance frequency of the resonator mode of the first acoustic resonator (10) or a resonance frequency of a resonator mode of the second acoustic resonator (20) is detected and the second light source (22) is modulated with the resonance frequency of the resonator mode of the second acoustic resonator (20), and Capturing the photoacoustic signal in the second acoustic resonator (20) with at least one second microphone (21) .

15. Method according to claim 14, characterized in that the first acoustic resonator (10) and the second acoustic resonator (20) are sequentially flowed through by the exhaled air (55).

16. Method according to claim 15, characterized in that acoustic crosstalk between the first acoustic resonator (10) and the second acoustic resonator (20) is reduced by an acoustic bandstop filter (8) and / or that the exhaled air (55) flows through at least one X / 4 tube (85) between the first acoustic resonator (10) and the second acoustic resonator (20).

17. Method according to one of claims 14 to 16, characterized in that the first photoacoustic measuring device (1) has two first light sources (12) which emit light at 308 nm and 295 nm and / or that the second photoacoustic measuring device (2) has two second light sources (22) which emit light at 295 nm and 275 nm.

18. Method according to one of claims 14 to 17, characterized in that the exhaled air is conveyed by a feed pump (50) via a supply line (51) through the first and second acoustic resonator (10, 20), wherein a pressure measuring device (52) and a throttle valve (53) are arranged in the supply line (51) and the flow rate is calculated from the pressure loss across the throttle valve (53).

19. Method according to one of claims 14 to 18, characterized in that the two trace gases are selected from propofol and acetone and / or that the concentration of the two trace gases in the exhaled air is determined by two independent differential absorption measurements.

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