# US 12,007,357 B2 · Electrochemical sensor

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- Number: US 12,007,357 B2
- Document ID: US12007357B2
- Status: Granted
- Kind: B2
- Application number: 17/938,157
- Filed: 2022-10-05
- Published: 2023-01-26
- Granted: 2024-06-11
- Earliest claimed: 2018-11-27
- Assignees: Endress+Hauser Conducta GmbH+Co. KG
- Applicants: Endress+Hauser Conducta GmbH+Co. KG
- Inventors: Andreas Löbbert; Michael Hanko; Matthäus Speck
- Web page: https://patentgrep.com/patent/US12007357B2

## CPC

- G01N 27/4163: {checking the operation of, or calibrating, the measuring apparatus (G01N27/3274, G01N27/4175 and G01N33/0006 take precedence)}
- G01N 21/78: producing a change of colour
- G01N 27/3335: {the membrane containing at least one organic component (G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001)}
- G01N 27/40: Semi-permeable membranes or partitions
- G01N 27/4161: {measuring the voltage and using a constant current supply, e.g. chronopotentiometry}
- G01N 27/36: Glass electrodes
- G01N 2021/6434: {Optrodes}
- G01N 2021/775: {Indicator and selective membrane}
- G01N 2021/7786: {Fluorescence}
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)

## Abstract

The present disclosure relates to an electrochemical sensor for determining a measurand correlating with a concentration of an analyte in a measuring fluid, comprising: a sensor membrane designed to be in contact with the measuring fluid for detecting measured values of the measurand; a probe housing which has at least one immersion region designed for immersion into the measuring fluid, wherein the sensor membrane is arranged in the immersion region of the probe housing; and a measurement circuit which is at least partially contained in the probe housing and is designed to generate and output a measurement signal dependent on the measurand, wherein the sensor membrane contains an optically detectable substance for marking the sensor membrane.

## Claims

### Claim 1

A method for testing a sensor membrane of an electrochemical sensor or of a membrane cap for an electrochemical sensor, the method comprising:
testing whether the sensor membrane contains an optically detectable substance using an optical detection method, wherein the testing comprises:
exciting the optically detectable substance to emit electromagnetic radiation;
detecting a signal of a radiation receiver configured to receive the emitted radiation from the optically detectable substance contained in the sensor membrane and transducing the emitted radiation into an electrical signal; and
determining whether the sensor membrane contains the optically detectable substance based on the electrical signal; and
estimating a remaining service life of the sensor membrane based on the testing.

### Claim 2 (depends on 1)

The method of claim 1, further comprising identifying the optically detectable substance based on the electrical signal.

### Claim 3 (depends on 2)

The method of claim 2, further comprising identifying the sensor membrane based on the identified optically detectable substance.

### Claim 4 (depends on 3)

The method of claim 3, further comprising confirming the identification of the sensor membrane by testing the sensor membrane using another optical method or a chemical method.

### Claim 5 (depends on 1)

The method of claim 1, further comprising confirming whether the sensor membrane contains the optically detectable substance by testing the sensor membrane using another optical method or a chemical method.

### Claim 6 (depends on 1)

The method of claim 1, wherein the exciting of the optically detectable substance includes radiating excitation radiation of one or more specific wavelengths from inside or outside of a probe housing of the electrochemical sensor upon the sensor membrane.

### Claim 7 (depends on 1)

The method of claim 1, wherein the optical detection method includes at least one of an optical luminescence measurement, an optical absorption measurement and an x-ray measurement.

### Claim 8 (depends on 1)

The method of claim 1, wherein the detected signal of the radiation receiver is at least one of an intensity change, a phase angle, a decay time, an absorption and a reflection of the emitted radiation.

### Claim 9 (depends on 1)

The method of claim 1, wherein the sensor is a potentiometric sensor.

### Claim 10 (depends on 9)

The method of claim 9, wherein the sensor membrane comprises a layer of an ion-selective glass that is doped with the optically detectable substance, or the sensor membrane comprises a first layer of an ion-selective glass and a second layer of a polymer doped with the optically detectable substance.

### Claim 11 (depends on 10)

The method of claim 10, wherein the sensor membrane comprises a first polymer matrix that is doped with the optically detectable substance.

### Claim 12 (depends on 11)

The method of claim 11, wherein the sensor membrane comprises a second polymer matrix containing at least one ionophore.

### Claim 13 (depends on 1)

The method of claim 1, wherein the sensor is an amperometric sensor.

### Claim 14 (depends on 13)

The method of claim 13, wherein the sensor membrane comprises a polymer that is permeable to the analyte or a reaction product of the analyte, wherein the polymer is doped with the optically detectable substance.

### Claim 15 (depends on 1)

The method of claim 1, wherein the optically detectable substance is selected from a group consisting of organometallic compounds, including at least one of: metal porphyrin complexes, polyaza annulene dyes, polyaza[18]annulene dyes, boron dipyrromethenes (BODIPY), azaborone dipyrromethenes (Aza-BODIPY), and metallophthalocyanine complexes.

### Claim 16 (depends on 1)

The method of claim 1, wherein the optically detectable substance is an upconversion material.

### Claim 17 (depends on 1)

The method of claim 1, wherein the optically detectable substance comprises one or more inorganic luminescent pigments that consist of an inorganic solid which itself exhibits donor-acceptor luminescence or charge transfer luminescence, or is doped with one or more luminescent ions, wherein the one or more luminescent ions are selected from the group consisting of In+, Sn2+, Pb2+, Sb3+, Bi3+, Ce3+, Ce4+, Pr3+, Nd3+, Sm2+, Sm3+, Eu2+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm2+, Tm3+, Yb2+, Yb3+, Ti3+, V2+, V3+, V4+, Mn2+, Mn3+, Mn4+, Fe3+, Fe4+, Fe5+, Co3+, Co4+, Ni2+, Cut, Ru2+, Ru3+, Pd2+, Ag+, Ir3+, Pt2+, and Au+.

### Claim 18 (depends on 1)

The method of claim 1, wherein the optically detectable substance comprises an electrochromic material.
