Electronic control of the pH of a solution close to an electrode surfaces

• US 10,379,080 B2
• Filed: 07/06/2015
• Issued: 08/13/2019
• Est. Priority Date: 07/06/2015
• Status: Active Grant

• Current Assignee: Robert Bosch GmbH
• Original Assignee: Robert Bosch GmbH
• Inventors: Johnson, Christopher, Kavusi, Sam, Fomina, Nadezda, Ahmad, Habib, Maruniak, Autumn, Lang, Christoph, Raghunathan, Ashwin
• Primary Examiner(s): Kessel, Maris R
• Application Number:
  US14/792,576
• Publication Number:
  US 20170010238A1
• Time in Patent Office: 1,499 Days
• CPC Class Codes: C12Q 1/001 Enzyme electrodes
• CPC Class Codes: G01N 27/302 pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes ion selective electrodes G01N27/333, glass electrodes G01N27/36
• CPC Class Codes: G01N 27/34 Dropping-mercury electrodes
• CPC Class Codes: G01N 27/36 Glass electrodes
• CPC Class Codes: G01N 27/4167 pH electrodes therefor G01N27/302, G01N27/36
• CPC Class Codes: G05D 21/02 characterised by the use of electric means

Abstract

Device and methods for use in a biosensor comprising a multisite array of test sites, the device and methods being useful for modulating the binding interactions between a (biomolecular) probe or detection agent and an analyte of interest by modulating the pH or ionic gradient near the electrodes in such biosensor. An electrochemically active agent that is suitable for use in biological buffers for changing the pH of the biological buffers. Method for changing the pH of biological buffers using the electrochemically active agents. The methods of modulating the binding interactions provided in a biosensor, analytic methods for more accurately controlling and measuring the pH or ionic gradient near the electrodes in such biosensor, and analytic methods for more accurately measuring an analyte of interest in a biological sample.

Claims

1. A method for controlling a pH of a solution using two or more electrodes, the method comprising:

a. measuring an open circuit potential (OCP) of the two or more electrodes in the solution while no current is being applied between the two or more electrodes;

b. determining a first pH of the solution based on the measured OCP of the two or more electrodes in the solution;

c. selecting an amount of current based on the measured OCP; and

d. providing the selected amount of current to the solution, thereby changing the pH of the solution to a second pH different than the first pH by electrochemically generating and/or consuming hydrogen ions,

wherein the two or more electrodes comprise a sense electrode and a reference electrode, the sense electrode is configured to also function as a working electrode, and the reference electrode is configured to also function as a counter electrode.

2. The method of claim 1, wherein electrochemically generating and/or consuming hydrogen ions is achieved by an electrochemical reaction of one or more redox active species in the solution.

3. The method of claim 2, wherein the one or more redox active species is selected from the group consisting of:

quinones, catechols, aminophenols, hydrazines, derivatives thereof, and combinations thereof.

4. The method of claim 2, wherein the one or more redox active species is a quinone selected from the group consisting of:

hydroquinone, benzoquinone, naphthaquinone, derivatives thereof, and combinations thereof.

5. The method of claim 1, wherein the two or more electrodes are each independently made of a material selected from the group consisting of:

metal oxide, gold, glassy carbon, graphene, silver, platinum, silver chloride, normal hydrogen, mercury drop, saturated calomel, and combinations thereof.

6. The method of claim 1, wherein the solution is buffered, aqueous, organic, or a mixture thereof.

7. The method of claim 1, wherein the solution is unbuffered.

8. The method of claim 1, wherein selecting the amount of current comprises selecting an electrical waveform, and wherein providing the selected amount of current to the solution comprises providing the electrical waveform to the solution.

9. The method of claim 8, wherein the selection of the electrical waveform is based on the determined first pH.

10. The method of claim 8, wherein the electrical waveform is a galvanostatic waveform or a potentiostatic waveform.

11. The method of claim 8, wherein the electrical waveform is selected from a predetermined map that maps respective current amounts to respective electrical waveforms.

12. A method for monitoring pH of a solution using a sense electrode and a reference electrode, wherein the sense electrode is configured to also function as a working electrode and the reference electrode is configured to also function as a counter electrode, the method comprising:

a. selecting a target open circuit potential (OCP) based on a target pH for the solution;

b. characterizing an OCP of the solution between the reference electrode and the sense electrode while no current is being applied to the sense electrode; and

c. iteratively performing the following;

i. selecting an amount of current to be applied to the sense electrode in order to minimize a difference between the OCP of the solution and the target OCP;

ii. applying the selected amount of current to the sense electrode to adjust the OCP of the solution; and

iii. measuring the OCP of the solution.

13. The method of claim 12, wherein the solution is an aqueous solution.

14. The method of claim 12, wherein the target pH is set by incorporating an electro-chemical delta-sigma-modulator.

15. The method of claim 14, wherein the output-signal of the electro-chemical delta-sigma-modulator is digitally filtered to get a digital representation of the charge needed to create the target pH.

16. The method of claim 12, wherein the target OCP is a range with an upper bound and a lower bound.

17. The method of claim 12, wherein the target pH is a single target value.

18. The method of claim 12, wherein the amount of current applied to the sense electrode is provided by applying an electrical waveform.

19. The method of claim 18, wherein the electrical waveform is a galvanostatic waveform or a potentiostatic waveform.

20. The method of claim 18, wherein the electrical waveform is selected from a predetermined map that maps respective current amounts to respective electrical waveforms.

21. The method of claim 12, wherein the sense electrode is coated with a pH sensitive coating.

22. The method of claim 21, wherein the pH sensitive coating is an organic material.

23. The method of claim 21, wherein the pH sensitive coating is an inorganic material.

24. The method of claim 21, wherein the pH sensitive coating is made from a material selected from the group consisting of:

polyaniline, polypyrrole, iridium oxide, and combinations thereof.