Raman spectroscopic system with integrating cavity

• US 6,975,891 B2
• Filed: 12/21/2001
• Issued: 12/13/2005
• Est. Priority Date: 12/21/2001
• Status: Expired due to Fees

• Current Assignee: Covidien LP (Medtronic Plc)
• Original Assignee: NIR Diagnostics Incorporated
• Inventors: Pawluczyk, Romuald
• Primary Examiner(s): WINAKUR, ERIC FRANK
• Application Number:
  US10/032,145
• Publication Number:
  US 20030120137A1
• Time in Patent Office: 1,453 Days
• Field of Search: 600/310, 600/317, 600/316, 600/476, 356/301, 356/215, 356/236, 250/339.07, 250/339.12, 250/340
• US Class Current: 600/310
• CPC Class Codes: A61B 5/14532 for measuring glucose, e.g. by tissue impedance measurement
• CPC Class Codes: A61B 5/14546 for measuring analytes not otherwise provided for, e.g. ions, cytochromes
• CPC Class Codes: A61B 5/1455 using optical sensors, e.g. spectral photometrical oximeters
• CPC Class Codes: A61B 5/6826 Finger
• CPC Class Codes: A61B 5/6838 Clamps or clips
• CPC Class Codes: G01N 2021/651 Cuvettes therefore
• CPC Class Codes: G01N 21/65 Raman scattering
• CPC Class Codes: G01N 2201/06126 Large diffuse sources
• CPC Class Codes: G01N 2201/065 Integrating spheres

Abstract

The present invention provides an apparatus for measurement of Raman scattered radiation comprising. The apparatus comprises at least one source of electromagnetic radiation for producing an electromagnetic radiation beam characterized by a narrow spectral width, an integrating cavity having an interior and an exterior, wherein a sample is placed in said interior. The integrating cavity further having at least one port for insertion of the sample in the interior and for transmission of the electromagnetic radiation into and out from the interior, the at least one port extending from the exterior to said interior of said integrating cavity. The integrating cavity also comprises a first optical element for transmitting the electromagnetic radiation into the interior of the integrating cavity through the at least one port, and a second optical element for collecting Raman scattered electromagnetic radiation from the sample through the at least one port. The apparatus also comprises a spectrum analyzer for determining spectral composition of the Raman scattered electromagnetic radiation, a detector for measuring the Raman scattered electromagnetic radiation; and a system for determining concentration of at least one chemical compound from the measured Raman scattered electromagnetic radiation. The apparatus may also comprise a radiation expanding element. A method for measuring the concentration of one or more chemical compounds in a sample using Raman scattering is also provided.

Claims

1. An apparatus for measurement of Raman scattered radiation comprising:

a) one or more than one source of electromagnetic radiation for producing an electromagnetic radiation beam characterized by a narrow spectral width;

b) an integrating cavity comprising;

(i) an interior and an exterior, wherein a sample is placed in said interior, said integrating cavity having one or more than one port for insertion of said sample in said interior and for transmission of said electromagnetic radiation into and out from said interior, said one or more than one port extending from said exterior to said interior of said integrating cavity, and

(ii) a radiation expanding element for expanding said electromagnetic radiation before said electromagnetic radiation beam comes into contact with said sample;

c) a first optical element for transmitting said electromagnetic radiation into said interior of said integrating cavity through said one or more than one port;

d) a second optical element for collecting Raman scattered electromagnetic radiation from said sample through said one or more than one port;

e) a spectrum analyzer for determining spectral composition of said Raman scattered electromagnetic radiation;

f) a detector for measuring said Raman scattered electromagnetic radiation; and

g) a system for determining a concentration of one or more than one chemical compound in said sample from Raman scattered electromagnetic radiation measured by said detector.

2. The apparatus according to claim 1 wherein said source of electromagnetic radiation is selected from the group consisting of a laser, a light emitting diode (LED) and a superluminescent diode.

3. The apparatus according to claim 1, wherein said integrating cavity comprises electromagnetic radiation scattering material of sufficient thickness to back scatter a sufficient amount of electromagnetic radiation into said interior of said integrating cavity to enhance production, and analysis, of Raman scattered radiation with said spectrum analyzer and detector.

4. The apparatus according to claim 3, wherein said electromagnetic radiation scattering material comprises electromagnetic radiation scattering material selected from the group consisting of:

an electromagnetic radiation scattering opalescent glass, an electromagnetic radiation scattering material comprising polytetrafluoroethylene (PTFE), and an electromagnetic radiation scattering ceramic.

5. The apparatus according to claim 1, wherein said interior is delimited by an internal surface which comprises an electromagnetic radiation scattering coating of sufficient thickness to back scatter a sufficient amount of electromagnetic radiation into said interior of said integrating cavity to enhance production and analysis of Raman scattered radiation with said spectrum analyzer and detector.

6. The apparatus according to claim 5, wherein said electromagnetic radiation scattering coating comprises an electromagnetic radiation scattering material selected from the group consisting of:

an electromagnetic radiation scattering material comprising polytetrafluoroethylene (PTFE) an electromagnetic radiation scattering ceramic, a layer of electromagnetic radiation scattering MgO, and BaSO₄.

7. The apparatus according to claim 1, wherein said interior is delimited by an internal surface comprising a redistribution structure and coated with one or more than one thin layer of an optical material that enhances reflection.

8. The apparatus according to claim 7, wherein said optical material is selected from a group consisting of:

aluminum, silver, gold, and multiple dielectric layers.

9. The apparatus according to claim 1, wherein said integrating cavity is made of a material transparent to electromagnetic radiation with an internal, an external or both internal and external surface comprising a redistribution structure, wherein said internal, said external, or both of said internal and external surface is covered with one or more than one layer of a reflection enhancing material selected from group consisting of:

aluminum, silver gold, and multiple dielectric layers.

10. The apparatus according to claim 1 wherein said first optical element and said second optical element are selected from the group consisting of a lens, a mirror, a radiation guiding element, and a combination thereof.

11. The apparatus according to claim 10 wherein said radiation guiding element is an optic fiber.

12. The apparatus according to claim 1, wherein said spectrum analyzer is selected from the group consisting of a spectrometer, a Fourier transform spectrometer, a turntable filter, an acousto-optic turntable, and a variable transmittance filter.

13. The apparatus according to claim 1 wherein said detector is selected from the group consisting of a linear diode array, a CCD, a photodiode, and a photomultiplier.

14. The apparatus according to claim 1, wherein said system for determining a concentration of one or more than one chemical compound in said sample from Raman scattered electromagnetic radiation measured by said detector comprises a computer comprising one or more than one calibration algorithm.

15. The apparatus according to claim 1, wherein said radiation expanding element is selected from a diffusion wall and a lens or a combination thereof.

16. The apparatus according to claim 15, wherein said diffusion wall comprises one or more than one aperture, said one or more than one aperture located outside a cross sectional area of said electromagnetic radiation impinging on said diffusion wall.

17. The apparatus according to claim 15, wherein said diffusion wall comprises a material selected from the group consisting of:

an electromagnetic radiation scattering material comprising polytetrafluoroethylene (PTFE), an electromagnetic radiation scattering ceramic, an electromagnetic radiation scattering opalescent glass, a coated glass, a coated fused silica, a coated quartz, a coated sapphire, a coated transparent plastic, an electromagnetic radiation non-absorbing material, and one or more of a material with a redistribution structure on one or both surfaces.

18. The apparatus according to claim 17, wherein said integrating cavity comprises two or more than two ports coupled to said first optical element.

19. The apparatus according to claim 17, wherein said integrating cavity comprises two or more than two ports coupled to said second optical element.

20. The apparatus according to claim 1, wherein said integrating cavity comprises two or more than two ports and wherein said first and said second optical element are each coupled with a different port.

21. The apparatus according to claim 1, wherein said radiation expanding element comprises one or more than one diffusing wall separating said interior of said integrating cavity into a diffusing chamber and a sample chamber, said sample chamber for receiving said sample, said diffusion chamber and said sample chamber each comprising one or more than one port extending from said exterior to said interior and wherein said first optical element is optically coupled with said diffusing chamber and said second optical element is optically coupled with said sample chamber.

22. The apparatus according to claim 21, wherein said diffusion wall comprises a material selected from the group consisting of an electromagnetic radiation scattering opalescent glass, an electromagenetic scattering material comprising polytetrafluoroethylene (PTFE), an electromagnetic radiation scattering ceramic, a coated glass, a coated fused silica, a coated quartz, a coated sapphire, a coated transparent plastic, an electromagnetic radiation non-absorbing material, and one or more of a material with a redistribution structure on one or both surfaces.

23. A method for measuring a concentration of one or more than one chemical compound in a sample using Raman scattering comprising:

a) placing said sample within an integrating cavity comprising;

i) an interior and an exterior, wherein a sample is placed in said interior of said integrating cavity, said integrating cavity having one or more than one port for insertion of said sample in said interior and for transmission of electromagnetic radiation into and out from said integrating cavity, said one or more than one port extending from said exterior to said interior of said integrating cavity, and

ii) a radiation expanding element for expanding said electromagnetic radiation beam before said electromagnetic radiation comes into contact with said sample;

b) generating an electromagnetic radiation beam characterized by a narrow spectral width and transmitting said electromagnetic radiation into said integrating cavity;

c) directing said electromagnetic radiation beam through said integrating cavity so that before said electromagnetic radiation beam comes into contact with said sample an expanded beam having a specific radiation power density smaller than a predetermined tolerance limit for said sample is produced;

d) collecting Raman scattered electromagnetic radiation from said sample within said integrating cavity;

e) spectrally decomposing said Raman scattered electromagnetic radiation;

f) measuring said Raman scattered electromagnetic radiation; and

g) determining said concentration of said one or more than one chemical compound.

24. The method according to claim 23, wherein said sample is a digit.

25. The method according to claim 24, wherein said digit is a finger.

26. The method according to claim 25, wherein said one or more than one chemical compound is glucose.

27. The method according to claim 23, wherein said radiation expanding element of said integrating cavity comprises one or more than one diffusing wall separating said interior of said integrating cavity into a diffusion chamber and a sample chamber, said diffusion chamber and said sample chamber each comprising one or more than one port extending from said exterior to said interior and wherein in step b) said sample is placed in said sample chamber, in step c) said electromagnetic radiation is transmitted into said diffusing chamber through said one or more than one port of said diffusing chamber and in step d) said Raman scattered electromagnetic radiation is collected from said sample through said one or more than one port of said sample chamber.

28. An integrating cavity comprising:

a) an interior and an exterior, wherein a sample is placed in said interior of said integrating cavity, said integrating cavity having one or more than one port for insertion of said sample in said interior and for transmission of electromagnetic radiation into and out of said integrating cavity, said one or more than one port extending from said exterior to said interior of said integrating cavity, and

b) a radiation expanding element for expanding said electromagnetic radiation before said electromagnetic radiation beam comes into contact with said sample.