Surface plasmon resonance chemical electrode

• US 5,858,799 A
• Filed: 10/25/1996
• Issued: 01/12/1999
• Est. Priority Date: 10/25/1995
• Status: Expired due to Fees

• Current Assignee: University of Washington
• Original Assignee: University of Washington
• Inventors: Saban, Stevan B., Yee, Sinclair S., Jung, Chuck C., Darling, Robert B.
• Primary Examiner(s): WALLENHORST, MAUREEN
• Application Number:
  US08/738,445
• Time in Patent Office: 809 Days
• Field of Search: 422/82.01, 422/82.02, 422/82.05, 422/82.09, 422/82.11, 436/73, 436/74, 436/149, 436/150, 436/151, 436/164, 436/165, 356/445, 356/447, 356/317, 356/318, 204/554, 204/556, 204/400, 204/403
• US Class Current: 436/164
• CPC Class Codes: G01N 21/553 and using surface plasmons fluorescence excitation G01N21/648; enhanced Raman G01N21/658
• CPC Class Codes: G01N 21/7703 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 Class Codes: G01N 27/42 Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte

Abstract

This disclosure describes new methods and devices for sensing redox-active analytes in solution. The invention combines a surface plasmon resonance (SPR) sensor and a chemical electrode sensor. A conducting layer which supports SPR is attached to a voltage source. The voltage source is also connected to a reference electrode, which is in the aqueous solution with the SPR sensor. As the voltage is varied, the analytes undergo oxidation and reduction at the surface of the conducting film. The current is measured, just as it would be in a standard chemical electrode, with current peaks appearing at different potentials indicating different ions in the solution. Unlike a standard chemical electrode, the surface of the conducting film is also used to excite a surface plasmon wave (SPW). The SPW provides new information which is not available from any standard chemical electrode, such as the effective index of refraction at the surface of the conducting film as the analytes are being oxidized and/or reduced. This additional source of information can be used to minimize the effects of overlapping stripping peaks and interspecies compound formation as well as determine the thickness of surface layers during measurements. Additionally, the simultaneous determination of reaction properties and optical properties of reaction products can provide additional information about the aqueous support solution such as the quantity and types of natural oxidants in solution, such as oxygen or hydroxides. The formation of oxides and hydroxides will lead to measurably different optical properties.

Claims

1. A method for performing stripping voltammetry whereby positive ions, negative ions, or redox-active analytes can be detected in a sample, comprising:

(a) contacting the sample with a first sensing area of a surface plasmon resonance sensor;

(b) introducing light into the surface plasmon resonance sensor whereby the light undergoes total internal reflection therein;

(c) either (1) first applying a negative voltage to the first sensing area for a time sufficient so that positive ions or redox-active analytes in the sample are reduced at a surface of the sensing area, after which the voltage is scanned in a positive direction or (2) first applying a positive voltage to the first sensing area for a time sufficient so that negative ions or redox-active analytes in the sample are oxidized at a surface of the sensing area, after which the voltage is scanned in a negative direction; and

(d) measuring a surface plasmon resonance signal as a function of voltage applied to the first sensing area.

2. A method according to claim 1 further comprising the step of:

(e) measuring current flow through the sensor as a function of applied voltage.

3. A method according to claim 1 for performing anodic stripping voltammetry to detect analytes in a sample, the method comprising the steps of:

(a) contacting the sample with the first sensing area of the surface plasmon resonance sensor;

(b) introducing light into the surface plasmon resonance sensor whereby the light undergoes total internal reflection therein;

(c) applying a negative voltage to the first sensing area for a time sufficient to allow for an analyte to be reduced at a surface of the first sensing area;

(d) scanning the voltage in a positive direction until the reduced analyte at least begins to be oxidized off the first sensing area; and

(e) measuring a surface plasmon resonance signal as a function of voltage applied to the first sensing area.

4. A method according to claim 1 for performing cathodic stripping voltammetry to detect analytes in a sample, the method comprising the steps of:

(a) contacting the sample with the first sensing area of the surface plasmon resonance sensor;

(b) introducing light into the surface plasmon resonance sensor whereby the light undergoes total internal reflection therein;

(c) applying a positive voltage to the first sensing area for a time sufficient to allow for an analyte to be oxidized at a surface of the first sensing area;

(d) scanning the voltage in a negative direction until the oxidized analyte at least begins to be reduced off the first sensing area; and

(e) measuring a surface plasmon resonance signal as a function of voltage applied to the first sensing area.

5. A method for detecting redox-active and redox-inactive analytes in a sample, comprising the steps of:

(a) contacting the sample with a first sensing area of a surface plasmon resonance sensor device, said device comprising;

a surface plasmon resonance sensor comprising an optical fiber having a core and a cladding layer surrounding the core, wherein the optical fiber has a first end and a second end and has a first sensing area located between the first end and the second end or at the second end, wherein the first sensing area is defined by a conducting film in contact with at least a portion of a surface of the core free from the surrounding cladding layer;

a light source optically coupled to the first end of the sensor such that light propagates by total internal reflection from the first end towards the second end and excites surface plasmon resonance;

a voltage source electrically coupled to the first sensing area for selectively applying a constant or variable voltage to the first sensing area; and

a detector for monitoring a surface plasmon resonance signal exiting the surface plasmon resonance sensor as a function of voltage applied to the first sensing area;

(b) introducing light into the surface plasmon resonance sensor whereby the light undergoes total internal reflection therein;

(c) applying a voltage to the first sensing area;

(d) measuring the surface plasmon resonance signal exiting the surface plasmon resonance sensor during or after application of the voltage to detect redox-inactive analytes; and

(e) measuring current resulting from application of the voltage or the surface plasmon resonance signal exiting the surface plasmon resonance sensor during or after application of the voltage to detect redox-active analytes.

6. A method for detecting intermetallic compound analytes, in a sample, comprising the steps of:

(a) contacting the sample with a first sensing area of a surface plasmon resonance sensor device, said device comprising;

a surface plasmon resonance sensor comprising an optical fiber having a core and a cladding layer surrounding the core, wherein the optical fiber has a first end and a second end and has a first sensing area located between the first end and the second end or at the second end, wherein the first sensing area is defined by a conducting film in contact with at least a portion of a surface of the core free from the surrounding cladding layer;

a light source optically coupled to the first end of the sensor such that light propagates by total internal reflection from the first end towards the second end and excites surface plasmon resonance;

a voltage source electrically coupled to the first sensing area for selectively applying a constant or variable voltage to the first sensing area; and

a detector for monitoring a surface plasmon resonance signal exiting the surface plasmon resonance sensor as a function of voltage applied to the first sensing area;

(b) introducing light into the surface plasmon resonance sensor whereby the light undergoes total internal reflection therein;

(c) applying a voltage to the first sensing area; and

(d) measuring the surface plasmon resonance signal exiting the surface plasmon resonance sensor during or after application of the voltage to detect intermetallic compound analytes.