Sensor for determining a measurand dependent upon a concentration of reactive oxygen species

Patent metadata

Field	Value
Publication number	US-10976291-B2
Application number	US-201715834120-A
Country	US
Kind code	B2
Filing date	Dec 7, 2017
Priority date	Dec 7, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

The present application discloses a sensor for determining a measurand correlated with a concentration of at least one analyte belonging to the class of reactive oxygen species in a measuring fluid, the sensor including a sensor element having an indicator substance, wherein the indicator substance is oxidized into an oxidized form of the indicator substance by the at least one analyte, a means for generating a flow of current in the sensor element that causes a reduction of the oxidized form of the indicator substance and thereby regeneration of the indicator substance, an optical measuring sensor to detect measuring radiation influenced by the oxidized form of the indicator substance and to generate an electrical measuring signal using the influenced measuring radiation, and a sensor switch connected to the optical measuring sensor to receive the measuring signal and to ascertain a measured value of the measurand using the measuring signal.

First claim

The invention claimed is:

1. A sensor for determining a measurand correlated with a concentration of at least one analyte in a measuring fluid, comprising:
a housing;
a sensor element disposed in the housing and extending at least to an exterior surface of the housing as to contact the measuring fluid, the sensor element including a membrane that contains an indicator substance, wherein the indicator substance is oxidized into an oxidized form of the indicator substance by the at least one analyte in the measuring fluid, wherein the at least one analyte is one of a class of reactive oxygen species;
at least two electrodes in electrical contact with the sensor element;
a voltage source disposed in the housing, connected to the at least two electrodes and adapted to generate a current flow in the sensor element sufficient to cause a reduction of the oxidized form of the indicator substance and thereby a regeneration of the indicator substance;
an optical measuring sensor disposed in the housing and configured to generate excitation radiation directed toward the sensor element and to detect measuring radiation from the sensor element, the measuring radiation effected by the oxidized form of the indicator substance under influence of the excitation radiation, the optical measuring sensor further configured to generate an electrical measuring signal based on the measuring radiation detected by the optical measuring sensor; and
a sensor circuit disposed in the housing, connected to the optical measuring sensor and configured to receive the measuring signal and to process the measuring signal to ascertain a measured value of the measurand using the measuring signal.

2. The sensor of claim 1 , wherein, to generate the measuring signal, the optical measuring sensor is configured to detect an intensity and/or a phase angle shift, and/or a decay time, and/or a wavelength shift of the detected measuring radiation.

3. The sensor of claim 1 , wherein the at least one analyte is hydrogen peroxide.

4. The sensor of claim 1 , wherein the indicator substance includes an organic or inorganic electrochromic substance.

5. The sensor of claim 4 , wherein the indicator substance has the composition K n M1 m [M2 o (CN) 6 ] p , wherein:
K is selected from a group consisting of Li, Na, K, Rb, Cs, and NH 4 ;
M1 and M2 are selected from a group of metals consisting of Fe, Co, Ni, Mn, Cd, Cu, Cr, V, and Ru; and
M1 and M2 are metals that are the same or different from each other.

6. The sensor of claim 1 , wherein the indicator substance is thermally stable up to at least a temperature of 140° C.

7. The sensor of claim 1 , wherein the voltage source includes at least one converter element in contact with the indicator substance, the at least one converter element configured to convert mechanical, optical, or thermal energy into a voltage or current.

8. The sensor of claim 1 , wherein the voltage source includes a plurality of piezo crystals in contact with the indicator substance and embedded in the sensor element.

9. The sensor of claim 1 , wherein the voltage source includes a Peltier element in contact with the indicator substance.

10. The sensor of claim 1 , wherein the voltage source includes an electrochromic substance that converts an external light pulse into current.

11. The sensor of claim 1 , wherein the at least two electrodes contact the indicator substance of the sensor element, wherein the voltage source is connected to the at least two electrodes in an electrically conductive manner and configured to apply a voltage between the electrodes.

12. The sensor of claim 11 , the sensor further comprising a voltage controller connected to the voltage source and configured to cause a pre-specified voltage between the at least two electrodes as a function of time.

13. The sensor of claim 11 , wherein the at least two electrodes include at least one metal, a semiconductor material, or a conductive polymer.

14. The sensor of claim 13 , wherein the at least one metal includes copper, silver, platinum, gold, or carbon, and the semiconductor material includes indium tin oxide (ITO) or LiWoO 3 .

15. The sensor of claim 11 , wherein a first electrode of the at least two electrodes covers at least part of a first side of the membrane, and a second electrode covers at least part of a second side of the membrane.

16. The sensor of claim 15 , wherein the first electrode is transparent to the measuring radiation and the influenced measuring radiation and is impermeable to the at least one analyte and/or the measuring fluid.

17. The sensor of claim 15 , wherein the second electrode has a network structure that is permeable to at least the at least one analyte and/or the measuring fluid.

18. The sensor of claim 11 , wherein the sensor element includes a sensor face defining at least a portion of an exterior of the sensor, and wherein a geometry of a second electrode of the at least two electrodes determines a shape and/or properties of the sensor face such that the shape of the sensor face inhibits the accumulation of gas bubbles or impurities.

19. The sensor of claim 11 , wherein the sensor circuit is configured to ascertain a current strength of a current flowing between a first electrode and a second electrode of the at least two electrodes at a pre-specified voltage and, using the ascertained current strength, to determine the measurand, or another measurand different from the measurand.

20. The sensor of claim 19 , wherein the sensor circuit is configured to simulate a value of the measurand by applying a pre-specified voltage over a pre-specified period, via a three-electrode circuit, to the membrane and to ascertain a measured value of the simulated measurand using the optical measuring sensor, the sensor circuit further configured to perform a calibration, verification, or adjustment of the sensor using the ascertained measured value.

21. A measuring device, comprising:
a housing;
a sensor configured to determine a measurand that correlates with a concentration of at least one analyte that belongs to a class of reactive oxygen species in a measuring fluid, the sensor comprising:
a sensor element disposed in the housing and extending at least to an exterior surface of the housing as to contact the measuring fluid that includes, the sensor element including a membrane that contains an indicator substance, wherein the indicator substance is oxidized into an oxidized form of the indicator substance by the at least one analyte in the measuring fluid;
at least two electrodes in electrical contact with the sensor element;
a voltage source disposed in the housing, connected to the at least two electrodes and adapted to generate a current flow in the sensor element sufficient to cause a reduction of the oxidized form of the indicator substance and thereby a regeneration of the indicator substance;
an optical measuring sensor disposed in the housing and configured to generate excitation radiation directed toward the sensor element and to detect measuring radiation from the sensor element, the measuring radiation effected by the oxidized form of the indicator substance under influence of the excitation radiation, the optical measuring sensor further configured to generate an electrical measuring signal based on the measuring radiation detected by the optical measuring sensor; and
a sensor circuit disposed in the housing, connected to the optical measuring sensor and configured to receive the measuring signal and to process the measu

Assignees

• Endress Hauser Conducta Gmbh Co Kg

Inventors

• Löbbert Andreas
• Scholz Katrin

Classifications

• G01N21/8507

  Probe photometers, i.e. with optical measuring part dipped into fluid sample · CPC title

• G01N21/78 Primary

  producing a change of colour · CPC title

• G01N2021/6434

  Optrodes · CPC title

• G01N2021/772

  Tip coated light guide · CPC title

• G01N21/7703

  using reagent-clad optical fibres or optical waveguides (using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B) · CPC title