Standardization methods for correcting spectral differences across multiple spectroscopic instruments

• US 7,881,892 B2
• Filed: 01/23/2006
• Issued: 02/01/2011
• Est. Priority Date: 01/21/2005
• Status: Active Grant

• Current Assignee: University Of Massachusetts
• Original Assignee: University Of Massachusetts
• Inventors: Soyemi, Olusola O., Soller, Babs R.
• Primary Examiner(s): Bui; Bryan
• Application Number:
  US11/337,912
• Publication Number:
  US 20070112258A1
• Time in Patent Office: 1,835 Days
• Field of Search: 702/76, 702/77, 702/85, 356/325, 356/326, 356/328
• US Class Current: 702/85
• CPC Class Codes: A61B 5/0059 using light, e.g. diagnosis by transillumination, diascopy, fluorescence A61B5/0093, A61B5/1455, A61B5/02416 and A61B5/0261 take precedence
• CPC Class Codes: A61B 5/14532 for measuring glucose, e.g. by tissue impedance measurement
• CPC Class Codes: A61B 5/14551 for measuring blood gases
• CPC Class Codes: A61B 5/1495 Calibrating or testing of in-vivo probes
• CPC Class Codes: G01J 2003/2866 Markers; Calibrating of scan
• CPC Class Codes: G01J 3/02 Details
• CPC Class Codes: G01J 3/0218 using optical fibers
• CPC Class Codes: G01J 3/0232 using shutters
• CPC Class Codes: G01J 3/0264 Electrical interface; User interface
• CPC Class Codes: G01J 3/0272 Handheld
• CPC Class Codes: G01J 3/0278 Control or determination of height or angle information for sensors or receivers
• CPC Class Codes: G01J 3/10 Arrangements of light sources specially adapted for spectrometry or colorimetry
• CPC Class Codes: G01J 3/28 Investigating the spectrum using colour filters G01J3/51
• CPC Class Codes: G01N 21/274 Calibration, base line adjustment, drift correction
• CPC Class Codes: G01N 21/31 Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry G01N21/72 takes precedence

Abstract

The invention relates to systems and methods for measuring properties of samples with standardized spectroscopic systems. The methods can include (i) measuring, with a first spectroscopic system, spectra of at least three different reference targets; (ii) calibrating the first spectroscopic system; (iii) measuring, with the first spectroscopic system, a spectrum of a known reference specimen having a known value of the property; (iv) generating a model for the measured property using the spectrum of the known reference specimen; (v) measuring, with a second spectroscopic system, the spectra of at least three different reference targets; (vi) calibrating the second spectroscopic system; (vii) applying the model to the second spectroscopic system; (viii) measuring a spectrum of the sample using the second spectroscopic system; and (ix) determining a value of the property using the model.

Claims

1. A method of determining a value of a property of a sample with a spectroscopic system, the method comprising:

measuring, with a first spectroscopic system, spectra of a first set of at least three different reference targets, each having a known, unique reflectivity spectrum;

calibrating the first spectroscopic system based on the spectra of the first set of reference targets measured by the first spectroscopic system;

measuring, with the first spectroscopic system, a spectrum of a known reference specimen having a known value of a property;

generating a model for determining the property on the first spectroscopic system using the spectrum of the known reference specimen;

measuring, with a second spectroscopic system, spectra of a second set of at least three different reference targets, each having a known, unique reflectivity spectrum;

calibrating the second spectroscopic system based on the spectra of the second set of reference targets measured by the second spectroscopic system;

applying the model to the second spectroscopic system;

measuring a spectrum of a sample using the second spectroscopic system; and

determining a value of the property of the sample based on the spectrum of the sample measured by the second spectroscopic system using the model.

2. The method of claim 1, wherein calibrating the first spectroscopic system comprises calculating a set of calibration coefficients a₁, b₁, and c₁.

3. The method of claim 1, wherein calibrating the second spectroscopic system comprises calculating a set of calibration coefficients a₂, b₂, and c₂.

4. The method of claim 1, wherein the three different unique reflectivity spectra for the first set of targets are the same as the three different unique reflectivity spectra for the second set of targets.

5. The method of claim 1, wherein at least one of the three different unique reflectivity spectra for the first set of targets is different than one of the three different unique reflectivity spectra for the second set of targets.

6. The method of claim 1, wherein the first and second spectroscopic systems are calibrated using a wavelength standard prior to measuring the spectra of the reference targets.

7. The method of claim 6, wherein the wavelength standard is a mercury-argon lamp.

8. The method of claim 1, wherein the reflectivity spectra of the reference targets are traceable to a standard.

9. The method of claim 1, further comprising determining an optimum stand-off distance between a probe of the first and second spectroscopic systems and a reference target.

10. The method of claim 9, wherein determining an optimum stand-off distance comprises measuring a reflectance intensity as a function of a distance between the probe and the reference target, and selecting the distance at which the reflectance intensity is highest.

11. The method of claim 1, wherein the spectrum of the sample measured using the second spectroscopic system is corrected prior to determining a value of the property.

12. The method of claim 11, wherein the correction comprises normalizing the spectrum with a standard normal variate algorithm.

13. The method of claim 1, wherein the value of the property is determined using a modified Beer'"'"'s law equation.

14. The method of claim 1, wherein the sample comprises human tissue.

15. The method of claim 1, wherein the sample is selected from the group consisting of blood, urine, and saliva.

16. The method of claim 1, wherein the sample is selected from the group consisting of tissue, blood, agricultural products, pharmaceuticals, natural products, and petroleum.

17. The method of claim 1, wherein the sample is an in vitro sample.

18. The method of claim 1, wherein the sample is an in vivo sample.

19. The method of claim 1, wherein the property is an amount of hemoglobin in the sample.

20. The method of claim 1, wherein the property is oxygen saturation, content, or pressure in the sample.

21. The method of claim 1, wherein the property is a pH of the sample.

22. The method of claim 1, wherein the property is a concentration of lactate or glucose in the sample.

23. The method of claim 1, wherein the property is a concentration of sodium ions, potassium ions, or calcium ions in the sample.

24. The method of claim 1, wherein the reflectivities of the at least three different reference targets measured with the first spectroscopic system span a range from about 2% to about 99%.

25. The method of claim 1, wherein the reflectivities of the at least three different reference targets measured with the second spectroscopic system span a range from about 2% to about 99%.

26. The method of claim 1, wherein the reflectivities of the at least three different reference targets measured with the first spectroscopic system are about 2%, about 50%, and about 99%.

27. The method of claim 1, wherein the reflectivities of the at least three different reference targets measured with the second spectroscopic system are about 2%, about 50%, and about 99%.

28. A standardized spectroscopic system comprising:

a light source;

a spectrograph;

a probe for receiving light from the light source that is reflected by a target;

a processor configured to;

(a) direct the light source to shine incident light on at least three different reference targets;

(b) direct the spectrograph to obtain reflectivity spectra of the at least three different targets by measuring incident light that is reflected by the targets and received by the probe;

(c) calculate calibration constants from the reflectivity spectra; and

(d) prompt an operator to re-standardize the spectroscopic system after a selected time interval has elapsed since a previous standardization sequence; and

a memory for storing the calibration constants.

29. The system of claim 28, wherein the processor comprises computer program code having instructions that direct the processor to carry out the calculation of the calibration constants.

30. The system of claim 28, wherein the probe is a fiber optic probe.

31. The system of claim 28, further comprising at least one stand-off for maintaining the probe at a selected distance from the target.

32. The system of claim 28, wherein the processor is further configured to correct spectra obtained with the system using a standard normal variate algorithm.

33. The system of claim 28, wherein the processor is further configured to determine a value of a property of a sample by fitting a measured spectrum of the sample to a modified Beer'"'"'s law equation.

34. The system of claim 28, further comprising a translation stage coupled to a driver for transporting the at least three different reference targets past a fixed position of the probe.

35. The system of claim 28, further comprising a translation stage coupled to a driver for transporting the probe past a fixed position of the at least three different reference targets.

36. The system of claim 28, further comprising the at least three different reference targets.

37. The system of claim 28, wherein the processor is further configured to provide prompts to an operator performing a series of steps comprising a standardization sequence.

38. The system of claim 28, wherein the processor is further configured to automatically perform a series of steps comprising a standardization sequence without operator intervention.

39. A spectroscopic system, comprising:

a light source;

a spectrograph;

a probe for receiving light from the light source that is reflected by a target; and

a processor configured to;

(a) receive information comprising a model for determining a value of a property using a different spectroscopic system, wherein the model is determined by;

(i) measuring, with the different spectroscopic system, spectra of a first set of at least three different reference targets each having a known, unique reflectivity spectrum;

(ii) calibrating the different spectroscopic system based on the spectra of the first set of reference targets;

(iii) measuring, with the different spectroscopic system, a spectrum of a known reference specimen having a known value of the property; and

(iv) generating the model for determining the value of the property using the different spectroscopic system from the spectrum of the known reference specimen;

(b) measure spectra of a second set of at least three different reference targets each having a known, unique reflectivity spectrum;

(c) calibrate the spectroscopic system based on the spectra of the second set of reference targets;

(d) apply the model to the spectroscopic system;

(e) measure a spectrum of a sample using the spectroscopic system; and

(f) determine a value of the property in the sample based on the spectrum of the sample using the model.

40. The system of claim 39, further comprising at least one stand-off for maintaining the probe at a selected distance from the reference targets.

41. The system of claim 39, wherein the processor is further configured to correct spectra measured using the system using a standard normal variate algorithm.

42. The system of claim 39, wherein the processor is further configured to determine the value of the property in the sample by fitting the measured spectrum of the sample to a modified Beer'"'"'s law equation.

43. The system of claim 39, further comprising the second set of the at least three different reference targets.