From: Subject: United States Patent: 5708957 Date: Tue, 15 Jan 2008 14:53:22 -0600 MIME-Version: 1.0 Content-Type: multipart/related; type="text/html"; boundary="----=_NextPart_000_0000_01C85786.5F8FC170" X-MimeOLE: Produced By Microsoft MimeOLE V6.00.2900.3198 This is a multi-part message in MIME format. ------=_NextPart_000_0000_01C85786.5F8FC170 Content-Type: text/html; charset="Windows-1252" Content-Transfer-Encoding: quoted-printable Content-Location: http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.htm&r=1&f=G&l=50&s1=5708957.PN.&OS=PN/5708957&RS=PN/5708957 United States Patent: 5708957

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United States Patent 5,708,957
Chuang ,   et al. January 13, 1998 =
Optical sensor with radioluminescent light source =

Abstract

An optical sensor is disclosed which uses a radioluminescent light = source to=20 supply the incident radiation for detecting a selected substance in a = test=20 medium. The radioluminescent source includes a beta emitting radio = isotope which=20 energizes a co-immobilized luminophore to release light in a given = wavelength=20 for a chemical sensor operation. The radioluminescent source is coupled = with a=20 sensing matrix for detecting and quantifying the analyte of interest. = The=20 sensing matrix produces a characteristic signal based on either = absorbance or=20 fluorescence which varies according to the concentration of the selected = analyte=20 in the sample. A photodetector measures the resulting optical signal = from which=20 the analyte concentration is determined.

Inventors: Chuang; Han (Iowa City, = IA), Arnold;=20 Mark A. (Iowa City, IA)
Assignee: University of Iowa Research = Foundation=20 (Iowa City, IA)
Appl. No.: 08/597,509
Filed: February 2, = 1996

Current U.S. = Class: 422/82.07 ; = 422/82.05;=20 422/82.08; 422/82.09; 436/127; 436/145; 436/163; 436/164; = 436/172
Current International = Class:=20 C09K = 11/04 (20060101); C09K=20 11/00 (20060101); G01N 21/64 (20060101); G01N = 021/64 ();=20 C09K 011/04 ()
Field of Search: = 422/68.1,82.05,82.07,82.08,82.09,82.11=20 436/57,164,127,68,75,145,163,166,172,800 252/646,31.4P=20

References Cited [Referenced=20 By]
U.S. Patent Documents
3612866 October 1971 Stevens et al.
4810655 March 1989 Khalil et al.
4861727 August 1989 Hauenstein et al.
4889660 December 1989 Jensen et al.
4935632 June 1990 Hart
4997597 March 1991 Clough et al.
5100587 March 1992 Clough et al.
5151603 September 1992 Nakamura
5155046 October 1992 Hui et al.
5176882 January 1993 Gray et al.
5233194 August 1993 Mauze et al.
5272088 December 1993 Morlotti
5313485 May 1994 Hamil et al.
5496997 March 1996 Pope
5605171 February 1997 Tam

Other References

A Continuous, Implantable Lactate Sensor; = Baker,=20 Gough; Anal. Chem, 1995, 67, 1536-1540. .
Luminescence = Quenching=20 Behavior of an Oxygen Sensor Based on a Ru(II) Complex Dissolved = in=20 Polystyrene; Hartmann, Leiner, Lippitsch; Anal. Cheml 1995, 67, = 88-93.=20 .
Optical Fiber Sensor for Biological Oxygen Demand; = Preininger,=20 Kilmani, Wolfbeis; Anal. Chem. 1994, 66, 1841-1846. .
Optical = Triple=20 Sensor for Measuring pH, Oxygen and Carbon Dioxide; Weigl, = Holobar,=20 Trettnak, Klimant, Kraus, O'Leary, Wolfbeis, Journal of = Biotechnology 32,=20 (1994) 127-138. .
Solid State Radioluminescent Sources Using=20 Tritium-Loaded Zeolites, and Their Proposed Use as Process = Monitors; Gill,=20 Hawkins, Renschler; Fusion Technology, vol. 21, Mar. 1992.=20 .
Photophysics and Photochemistry of Oxygen Sensors Based on=20 Luminescent Transition-Metal Complexes; Carraway, Demas, DeGraff, = Bacon;=20 Anal. Chem. vol. 63, No. 4, Feb. 15, 1991. .
Oxygen Optrode for = Use in=20 a Fiber-Optic Glucose Biosensor; Moreno-Bondi, Wolfbeis, Leiner = and=20 Schaffar; ANal. Chem, 1990, 62, 2377-2380. .
Immobilized=20 Transition-Metal Complex; Bacon, Demas; Anal. Chem. 1987, 59, = 2780-2785.=20 .
Fiber Optical Fluorosensor for Determination of Halothane = and/or=20 Oxygen; Wolfbeis Posch, Kroneis, Anal. Chem 1985, 57, 2558-2561. = .
A=20 Fast Responding Fluorescence Sensor for Oxygen; Wolfbeis, = Offenbacher,=20 Kroncis, Marsoner, Mikrochimica Acta (Wein) 1984 I, 153-158..=20

Primary Examiner: Le; Long V.=20
Attorney, Agent or Firm: Woodard, Emhardt, Naughton = Moriarty=20 & McNett
Claims


What is claimed is:

1. An optical sensor for detecting a = selected=20 substance, comprising:

a radioluminescent light source, = including:=20

a radioactive constituent,

a phosphor constituent = energized by=20 radiation from said radioactive constituent to emit light;

a = sensing=20 matrix absorbing light from said radioluminescent light source to = produce an=20 optical characteristic, the optical characteristic changing upon = exposure of=20 said sensing matrix to the selected substance; and

a = photodetector=20 configured to detect the optical characteristic and provide a = corresponding=20 signal to indicate detection of the selected substance.

2. The = optical=20 sensor of claim 1, wherein:

said radioactive constituent = includes a beta=20 particle emitter; and

said sensing matrix has a luminophore = portion.=20

3. The optical sensor of claim 2, wherein the selected substance = includes O.sub.2, said phosphor constituent includes ZnS:Ag, said = luminophore=20 portion includes a ruthenium complex fluorophore, and the optical = characteristic=20 includes fluorescence.

4. The optical sensor of claim 2, wherein = the=20 selected substance is pH of a solution, said phosphor constituent = includes=20 Y.sub.2 O.sub.2 S:Eu, said luminophore portion includes Merck N9, and = the=20 optical characteristic includes color of said sensing matrix.

5. = The=20 optical sensor of claim 2, wherein the selected substance is CO.sub.2, = said=20 phosphor constituent includes Y.sub.3 (Al,Ga).sub.5 O.sub.12 :Ce, said=20 luminophore portion includes m-cresol purple, and the optical = characteristic=20 includes color of said sensing matrix.

6. The optical sensor of = claim 1,=20 wherein said sensing matrix has a luminophore portion and said = luminophore=20 portion includes a compound selected from the group consisting of:=20

Ru(dpp).sub.3 ;

Ru(phen).sub.3 ;

Merck N9; and=20

m-cresol purple.

7. The optical sensor of claim 1, = wherein said=20 radioactive constituent includes one of .sup.3 H, .sup.14 C, and = .sup.147 Pm and=20 said phosphor constituent includes one of Y.sub.2 O.sub.2 S:Eu, Y.sub.3=20 (Al,Ga).sub.5 O.sub.12 :Ce, and ZnS:Ag.

8. An optical sensing = system for=20 detecting concentration of a selected substance in a test medium, = comprising:=20

a radioluminescent source emitting light;

a sensing = matrix=20 exposed to the test medium, said sensing matrix absorbing light from = said=20 radioluminescent source to produce an optical characteristic, the = optical=20 characteristic varying in accordance with concentration of the selected=20 substance in the test medium; and

a photodetector configured to = detect=20 the optical characteristic and provide a corresponding signal to = indicate=20 concentration of the selected substance in the test medium.

9. = The=20 optical sensing system of claim 8, wherein said radioluminescent source=20 includes:

a radioactive material emitting beta particles; and =

a=20 phosphor material energized by beta particles from said radioactive = material to=20 emit light.

10. The optical sensing system of claim 8, wherein = said=20 photodetector includes a photodiode.

11. The optical sensing = system of=20 claim 8, wherein said photodetector includes a photomultiplier tube. =

12.=20 The optical sensing system of claim 8, further comprising an optical = filter=20 positioned between said sensing matrix and one of said radioluminescent = source=20 and said photodetector.

13. The optical sensing system of claim = 8,=20 further comprising a container enclosing said radioluminescent source, = said=20 container being positioned to define a test cell between said sensing = matrix and=20 said radioluminescent source, and said test cell being configured to = receive the=20 test medium.

14. The optical sensing system of claim 13, wherein = said=20 photodetector includes a photodiode, said sensing matrix includes a = membrane=20 coupled to the photodetector, said membrane has a surface exposed to the = test=20 medium, and further comprising:

a first light filter positioned = between=20 said container and said test cell;

a second light filter = positioned=20 between said membrane and said photodetector; and

a signal = processing=20 subsystem electrically coupled to said photodetector, said signal = processing=20 subsystem including a display for providing a indication of the = substance=20 concentration to an operator.

15. The optical sensing system of = claim 8,=20 further comprising:

a probe housing said radioluminescent = source, said=20 probe having:

an outer surface coupled to said sensing matrix, = said=20 sensing matrix having a sensing surface configured to contact said test = medium,=20

a mirror adjacent said radioluminescent source to reflect=20 electromagnetic radiation emitted therefrom,

a body configured = to=20 transmit light from said radioluminescent source to said sensing matrix; =

an optical fiber coupling said probe to said photodetector, said = optical=20 fiber and said probe being configured to transmit electromagnetic = radiation from=20 said sensing matrix to said photodetector;

an optical filter = positioned=20 between said photodetector and said radioluminescent source; and =

a=20 coating covering at least a portion of said sensing surface to prevent = intrusion=20 of ambient light.

16. An optical sensor for detecting a selected = substance in a test medium, comprising:

a radioluminescent = source=20 emitting light;

a sensing matrix having a fluorophore portion, = said=20 sensing matrix being exposed to the test medium, said sensing matrix = providing a=20 fluorescent emission in response to absorption of light from said=20 radioluminescent source; and

a photodetector detecting a first = intensity=20 of the fluorescent emission when the test medium does not include the = selected=20 substance and said photodetector detecting a second intensity of the = fluorescent=20 emission when the test medium includes the selected substance, said = second=20 intensity differing from said first intensity.

17. The optical = sensor of=20 claim 16, wherein said fluorophore portion includes a ruthenium complex. =

18. The optical sensor of claim 16, wherein said fluorophore = portion=20 includes a PAH compound.

19. The optical sensor of claim 16, = wherein=20 said sensing matrix includes one of:

Ru(dpp).sub.3 in a = polystyrene=20 membrane;

Ru(dpp).sub.3 in a sol-gel membrane; and=20

Ru(phen).sub.3 in a silicone membrane.

20. The optical = sensor of=20 claim 16, wherein said radioluminescent source includes:

a = radioactive=20 constituent emitting beta particles; and

a phosphor constituent = emitting=20 light in response to beta particles from said radioactive constituent.=20

21. The sensor of claim 16, further comprising:

a = container for=20 enclosing said radioluminescent source and being configured to transmit = light=20 from said radioluminescent source to said sensing matrix; and

a = coupling=20 means for positioning said sensing matrix relative to said container, = said=20 photodetector, and the test medium.

22. The optical sensor of = claim 1,=20 wherein said sensing matrix is spaced apart from said radioluminescent = light=20 source to define a test cell therebetween.

23. The optical = sensor of=20 claim 8, wherein said sensing matrix includes a film containing a = fluorophore=20 configured to detect oxygen, and said film is spatially separated from = said=20 radioluminescent light source.

24. The optical sensor of claim = 16,=20 wherein said sensing matrix includes a film with said fluorophore = portion, and=20 said film is spatially separated from said radioluminescent light = source.=20

25. An optical sensing system for detecting a selected = substance,=20 comprising:

a radioluminescent light source, including: =

a=20 radioactive constituent,

a phosphor constituent energized by = radiation=20 from said radioactive constituent to emit light;

a sensing = matrix=20 absorbing light from said radioluminescent light source, said sensing = matrix=20 being defined separately from said radioluminescent light source to = produce an=20 optical characteristic, said optical characteristic changing upon = exposure of=20 said sensing matrix to the selected substance; and

a = photodetector=20 configured to detect the optical characteristic and provide a = corresponding=20 signal to indicate detection of the selected substance.

26. The = system=20 of claim 25, wherein said radioluminescent light source and said sensing = matrix=20 are spaced apart from each other to define a test cell therebetween. =

27.=20 The system of claim 25, wherein said sensing matrix includes a film = containing a=20 luminophore and said film is spaced apart from said radioluminescent = light=20 source.

28. The system of claim 25, further comprising a probe = housing=20 said radioluminescent source, said probe having:

an outer = surface=20 coupled to said sensing matrix, said sensing matrix having a sensing = surface=20 configured to contact a test medium; and

a body configured to = transmit=20 light from said radioluminescent source to said sensing matrix, at least = a=20 portion of said body being positioned between said sensing matrix and = said=20 radioluminescent source.

29. The system of claim 28, wherein = said probe=20 includes a mirror to reflect electromagnetic radiation emitted from said = radioluminescent light source.

30. The system of claim 29, = further=20 comprising an optical fiber coupling said probe to said photodetector, = said=20 probe being configured to transmit electromagnetic radiation from said = sensing=20 matrix to said photodetector.

31. The system of claim 25, = wherein said=20 sensing matrix includes a ruthenium complex configured to detect oxygen. =

32. The system of claim 25, wherein said radioactive constituent = includes at least one of .sup.3 H or .sup.147 Pm.

33. The system = of=20 claim 25, wherein said phosphor constituent includes at least one of = Y.sub.2=20 O.sub.2 S:Eu, Y.sub.3 (Al,Ga).sub.5 O.sub.12 :Ce, or ZnS:Ag.
=20
Description


BACKGROUND OF THE INVENTION

A. Field of the Invention=20

The present invention relates to sensors which produce an = optical signal=20 to indicate the presence and/or concentration of a specified substance.=20

B. Description of the Prior Art

Optical sensors have = been used=20 to detect and quantify the presence of a substance of interest in a test = medium=20 through fluorescence quenching. By this approach, a source of light is = used to=20 stimulate fluorescence of a flourophore compound. The presence and/or=20 concentration level of the substance of interest can then be detected = due to the=20 quenching effect that the substance has on the intensity of the = fluorescence.=20

Fluorescence quenching has been used, particularly, to detect = and=20 quantify oxygen (O.sub.2) concentration. For such sensors, a ruthenium = based=20 compound or "ruthenium complex" has been used as the flourophore to = provide the=20 requisite fluorescence. The use of ruthenium complexes in oxygen sensors = have=20 been described in the following publications: Hartman, Leiner and = Lippitsch,=20 Luminescence Quenching Behavior of an Oxygen Sensor Based on a Ru(II) = Complex=20 Dissolved in Polystyrene, 67 ANAL. CHEM. 88 (1995); Carraway, Demas, = DeGraff,=20 and Bacon, Photophysics and Photochemistry of Oxygen Sensors Based on=20 Luminescent Transition-Metal Complexes, 63 ANAL. CHEM. 337 (1991); and = Bacon and=20 Demas, Determination of Oxygen Concentrations by Luminescence Quenching = of a=20 Polymer-Immobilized Transition-Metal Complex, 59 ANAL. CHEM. 2780 = (1987).=20

In addition to ruthenium complexes, other flourophores have also = been=20 used to detect oxygen, as described in the following publications: = Wolfbeis,=20 Posch and Kroneis, Fiber Optical Fluorosensor for Determination of = Halothan=20 and/or Oxygen, 57 ANAL. CHEM. 2556 (1985); and Wolfbeis, Offenbacher, = Kroneis=20 and Marsoner, A Fast Responding Fluorescence Sensor for Oxygen, I = MIKROCHIMICA=20 ACTA [WIEN] 153 (1984). U.S. Pat. Nos. 5,176,882 to Gray et al., = 5,155,046 to=20 Hui et al., and 4,861,727 to Hauenstein et al. also disclose various=20 flourophores which may be used to detect oxygen. As shown in several of = the=20 above cited references, substances besides oxygen can also be detected = through=20 the use of a fluorescence quenching mechanism.

More generally,=20 luminophores have been used to facilitate optical sensing. As used = herein, a=20 "luminophore" is a chemical species which reacts to the presence of a = substance=20 to produce an optical result. A flourophore is thus one type of = luminophore.=20 Another type of luminophore changes color in accordance with changes in = the=20 amount of a substance of interest. A sensor which utilizes this = principle to=20 detect pH and Co.sub.2 is disclosed in Weigl, Holobar, Trettnak, = Klimant, Kraus,=20 O'Leary, and Wolfbeis, Optical Triple Sensor for Measuring pH, Oxygen = and Carbon=20 Dioxide, 32 JOURNAL OF BIOTECHNOLOGY 127 (1994). =

Luminophore-based=20 sensors typically use a LED or lamp as a light source, requiring an = external=20 power supply which can add noise and variability to sensor operation due = to=20 variations in the supply power. Where the power supply has a limited = life, such=20 as when batteries are used as the power source, the operation of the = sensor is=20 limited by the operational lifetime of the power supply. The need to = provide a=20 power supply can thus be a limiting factor for many remote sensing = applications,=20 such as for chemical sensing during space missions where power is scarce = and=20 long term stability is required.

SUMMARY OF THE INVENTION =

As=20 described herein, there is provided an optical sensor which is = self-powered, and=20 which is therefore particularly suited for many applications where the=20 requirement for powering the sensing mechanism may be a limiting factor. = In the=20 following described preferred embodiment, an oxygen sensor is disclosed = which is=20 energized by a radioluminescent light source to detect a selected = substance in a=20 test medium. The sensor includes a luminophore matrix exposed to the = test medium=20 which absorbs light from the radioluminescent source. The sensing matrix = produces an optical characteristic in response to the absorption of = light from=20 the radioluminescent source which varies with the presence of the = selected=20 substance. A photodetector detects the optical characteristic and = provides a=20 corresponding signal to indicate detection of the selected substance in = the test=20 medium.

By one aspect of the present invention, an optical = sensor is=20 provided with a continuous and reliable source of light from the energy = released=20 by the decay of a radioactive isotope in a radioluminescent material. = The sensor=20 is particularly useful in remote sensing systems, such as in deep sea or = outer=20 space applications. Also, such a sensor generally provides a more = efficient and=20 reliable optical sensing system for any application.

By another = aspect=20 of the present invention, an optical sensor is provided with a = self-powered=20 light source by the use of a radioluminescent material which includes a=20 radioactive beta emitter constituent and a phosphor constituent = energized by=20 beta particles from the radioactive constituent to emit light. By = appropriate=20 selection of the phosphor compound, the wavelength of light produced by = the=20 radioluminescent source may be matched to a corresponding sensing matrix = to=20 optimally configure the sensor for the detection of a particular = substance of=20 interest.

As taught herein, an optical sensor is constructed = which=20 includes a sensing matrix that absorbs light from a radioluminascent = source to=20 produce an optical characteristic. The optical characteristic is = detected by a=20 photodedector which provides a corresponding signal. The optical = characteristic=20 and corresponding photodetector signal changes upon exposure of the = sensing=20 matrix to a selected substance. As used herein, "selected substance" = means any=20 type of chemical species, including, for example, O.sub.2, CO.sub.2, or = pH=20 level; and "optical characteristic" means any detectable property of the = sensing=20 matrix resulting from the absorption, reflection, or emission of = electromagnetic=20 radiation. Examples of optical characteristics include, but are not = limited to,=20 color, intensity of reflected or emitted light, and absorption or = emission=20 spectra.

Accordingly, one object of the present invention is to = provide=20 an optical sensor which has a self-powered light source.

Another = object=20 is to provide an optical sensing system with a self-powered light source = having=20 improved power efficiency, reliability, and long term operability. =

Still=20 another object of present invention is to provide an RL light source for = a=20 luminophore-based optical sensor which is optimally configured to detect = a=20 particular substance of interest.

Further objects, features, and = advantages of the present invention shall become apparent from the = detailed=20 drawings and descriptions provided herein.

BRIEF DESCRIPTION OF = THE=20 DRAWINGS

FIG. 1 is a schematic illustration of one preferred = embodiment=20 of an optical sensing system of the present invention;

FIG. 2 is = a=20 schematic illustration of one preferred embodiment of a probe sensor of = the=20 present invention;

FIG. 3 is an intensity-time profile for one = preferred=20 embodiment of an oxygen sensor of the present invention;

FIG. 4 = is a=20 calibration curve for the oxygen sensor profiled in FIG. 3; and =

FIG. 5=20 is a calibration curve for the oxygen sensor profiled in FIG. 3 with = improved=20 linearity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For = the=20 purposes of promoting an understanding of the principles of the = invention,=20 reference will now be made to the embodiment illustrated in the drawings = and=20 specific language will be used to describe the same. It will = nevertheless be=20 understood that no limitation of the scope of the invention is thereby = intended,=20 any alterations and further modifications in the illustrated device, and = any=20 further applications of the principles of the invention as illustrated = therein=20 being contemplated as would normally occur to one skilled in the art to = which=20 the invention relates.

FIG. 1 schematically illustrates an = optical=20 sensor system 1 of the present invention. System 1 includes signal = processing=20 subsystem 10 coupled to sensor 20 by coupling 25. Sensor 20 is depicted = in a=20 schematic sectional view and includes a radioluminescent light (RL) = source 30,=20 test cell 40, sensing matrix 50, and photodetector 60. RL source 30 is = enclosed=20 or housed in container 32 along with plug 36. Container 32 has top = portion 31=20 opposing transmission portion 33. Top portion 31 defines a closable = opening (not=20 shown) to facilitate placement of RL source 30 and plug 36 within = container 32.=20 Lid 35 provides for closure of container 32. Preferably, container 32 is = manufactured from a transparent glass.

RL source 30 includes a=20 radioactive isotope which supplies energy to produce light from = radioactive=20 decay. In one preferred embodiment, RL source 30 comprises a radioactive = constituent which emits beta particles and a phosphor constituent which = emits=20 light in response to bombardment by beta particles from the radioactive=20 constituent. The wavelength and intensity of light generated by this = embodiment=20 may be established by those skilled in the art by adjusting the type, = amount,=20 and relative orientation of the radioactive isotope and phophor = constituents.=20

Light emitted by RL source 30 is symbolically represented by = arrows 38.=20 Plug 36 is configured to contain the beta radiation and provide = mechanical=20 strength to RL source 30. Plug 36 may be a conventional epoxy compound.=20 Transmission portion 33 of container 32 is configured so that light from = RL=20 source 30 transmits therethrough. Optical filter 34 provides for the = selective=20 transmission of light from RL source 30 to test cell 40. As used herein, = "optical filter" means any device which may be used to transmit a = selected=20 wavelength or selected range of wavelengths of electromagnetic = radiation.=20

Test cell 40 includes opposing walls 42, 44 which define space = 45=20 configured to receive a test medium. A test medium enters test cell 40 = along a=20 pathway indicated by arrow 46 and exits the pathway along arrow 48. Test = cell=20 wall 42 is configured to permit the transmission of light from optical = filter 34=20 therethrough. Light also passes through space 45 containing the test = medium=20 before encountering sensing matrix 50. For this configuration, the test = medium=20 is a gas or liquid which permits the transmission of light therethrough. = In=20 other embodiments, the test cell may be configured to define a space = configured=20 to receive a test medium without walls or a particular pathway. For = example,=20 filter 34 and sensing matrix 50 may be positioned to define an = appropriate test=20 cell therebetween.

Sensing matrix 50 has sensing surface 52 = adjacent=20 space 45. Sensing matrix 50 is stimulated by the absorption of light = transmitted=20 from RL source 30. Preferably, sensing matrix 50 is permeable to = facilitate=20 detection of a desired substance in a test medium contained within test = cell 40=20 via sensing surface 52. In one preferred embodiment, sensing matrix 50 = is=20 configured to immobilize a luminophore compound within a membrane or = film which=20 is permeable to the substance of interest. This configuration reduces = abrasion=20 and leaching of the luminophore compared to direct exposure on sensing = surface=20 52 exposed to the test medium. However, in other embodiments, the = sensing matrix=20 may include a luminophore on a surface and the sensing matrix = configuration may=20 be other than a membrane or film.

Sensing matrix 50 produces an = optical=20 characteristic which varies with the presence of a selected substance in = test=20 cell 50. This varying optical characteristic is represented by arrows 58 = and is=20 detected by photodetector 60 through optical filter 64. For one = embodiment, this=20 optical characteristic is the intensity of light detected by = photodetector 60 as=20 a function of sensing matrix color. For another embodiment, this optical = characteristic includes fluorescence intensity of the sensing matrix.=20

Photodetector 60 provides a signal corresponding to the optical=20 characteristic which is input to signal processing subsystem 10 via = coupling 25.=20 Subsystem 10 is schematically depicted and processes the input sensor = signal to=20 provide sensing information using conventional techniques. Subsystem 10 = includes=20 signal conditioning portion 12 which may provide signal filtering, = amplication,=20 linearization, and other conventional signal conditioning. Subsystem 10 = also=20 includes display 14 to provide sensing information to an operator. A = recording=20 device 16 is also shown which may be used to record sensing information = derived=20 from the photodetector signal. This record may include the photodetector = signal=20 relative to another parameter such as time or test medium flow rate = through test=20 cell 40.

Photodetector 60 may be a photomultiplier tube or = photodiode of=20 a conventional type electrically connected to subsystem 10 by coupling = 25.=20 Coupling 25 schematically corresponds to the type of photodetector 10 = selected=20 and typically will include multiple electrical interconnections. = Subsystem 10=20 may be configured for electronic, electrical, mechanical, and = electromechanical=20 devices of a conventional type which are interconnected to meet sensor = detection=20 and analysis requirements. Preferably, subsystem 10 is a programmable=20 microprocessor-based system and signal conditioning portion 12 includes=20 appropriate analog to digital conversion circuitry. In one embodiment, = subsystem=20 10 includes a calibration means (not shown). Preferably, subsystem 10 = may be=20 adapted for use with multiple sensors.

One configuration of the=20 preferred embodiment of sensing system 1 is next discussed which is = particularly=20 designed to detect oxygen. For this configuration, RL source 30 of = sensor 20=20 includes .sup.147 Pm as the radioactive constituent and ZnS:Ag as the = phosphor=20 constituent. Beta particles from the radioactive decay of the .sup.147 = Pm=20 isotope energize the ZnS:Ag phosphor to produce blue light. This light = is=20 transmitted through transmission portion 33, optical filter 34, wall 42, = and=20 space 45 to sensing matrix 50.

Sensing matrix 50 has a = flourophore=20 portion that emits fluorescent light in response to the absorption of = blue light=20 from RL source 30. This flourophore is the ruthenium complex=20 tris(4,7-diphenyl-1, 10-phenanthroline) ruthenium (II) chloride = (Ru(dpp).sub.3).=20 Preferably, sensing matrix 50 for this embodiment further includes an = oxygen=20 permeable Polyvinyl Chloride (PVC) membrane in which the ruthenium = complex is=20 immobilized. Flourescence from the flourophore portion is quenched by = O.sub.2.=20 When a test medium with O.sub.2 passes through test cell 40 along arrows = 46, 48,=20 the intensity of the fluorescence emitted by sensing matrix 50 decreases = with=20 increasing O.sub.2 concentration. The intensity of the fluorescence = emission=20 provides an optical characteristic indicative of O.sub.2 concentration = which is=20 detected by photodetector 60. Photodetector 60 inputs a corresponding = signal to=20 subsystem 10. Subsystem 10 conditions the signal and provides a display = and=20 record of information corresponding to the signal. For this = configuration,=20 optical filters 34 and 64 are used to improve linearity of the sensor by = reducing stray radiation. Filter 34 selectively passes light to excite = the=20 fluorophor while filter 64 passes only the light emitted from the = excited=20 fluophore.

FIG. 2 shows sensor 120 of the present invention = depicted in=20 a partial schematic sectional view. Sensor 120 includes RL source 130 = housed=20 within probe 132. Probe 132 has generally cylindrical probe body 136 = with tip=20 131 opposing base 133. Preferably probe body 136 is formed from = transparent=20 glass. RL source 130 is optically coupled to probe body 136 via optical = filter=20 134. Mirror 135 is positioned at tip 131 of probe 132 to reflect light = from RL=20 source 130 into probe body 136.

RL source 130 emits light into = probe=20 body 136 as represented by arrows 138. At least a portion of this light = is=20 absorbed by sensing matrix 150 configured as a cylindrical membrane = coupled to=20 outer surface 139 of probe 132. Sensing surface 152 of sensing matrix = 150 is at=20 least partially covered by coating 154 to block ambient light. Other = embodiments=20 may not include coating 154. In one embodiment, coating 154 is an opaque = silicone compound.

Probe 132 is configured for exposure to a = test medium=20 including the substance or substances to be detected by sensor 120. = Notably, the=20 test medium need not transmit light to sensing matrix 150. Sensing = matrix 150=20 responds to the presence of the selected substance to provide a = detectable=20 optical characteristic. Arrows 158 represent this optical = characteristic. This=20 optical characteristic is detected by photodetector 160. Optical filter = 164 and=20 optical fiber 166 are coupled to sensing matrix 150 and photodetector = 160 to=20 transmit the optical characteristic from probe 132 to photodetector 160. = Photodetector 160 provides a signal corresponding to the optical = characteristic.=20 A signal processing subsystem (not shown) similar to subsystem 10 shown = in FIG.=20 1 may be used to process a signal from photodetector 160 via appropriate = electrical coupling.

Sensor 120 may be configured to detect = oxygen using=20 an RL source 130 that includes .sup.147 Pm and phosphor ZnS:Ag to = generate blue=20 light. This light may be used to excite a ruthenium complex flourophore=20 contained in sensing matrix 150. Fluorescent intensity indicative of = oxygen=20 quenching may be detected by photodetector 160 via optical filter 164 = and=20 optical fiber 166. Optical fiber 166 is depicted with a break to = schematically=20 represent the relative greater length of optical fiber 166 compound to = probe 132=20 in typical applications.

Sensing matrix 150 and coating 154 are=20 configured to permit the passage of the substance being detected to the=20 flourophore portion of the sensor. Coating 154 is preferably opaque to = reduce=20 the amount of ambient light reaching the sensing matrix through the test = medium=20 and thereby improve noise immunity of system 101. Optical filters 134 = and 164=20 are used to improve sensor 120 linearity and reduce optical noise from=20 background radiation.

Referring generally to FIGS. 1 & 2,=20 photodetector 60, 160 may be a photomultiplier tube, photodiode, or = other type=20 of photodetection device as would occur to those skilled in the art. In = other=20 embodiments, fewer or more optical filters 34, 64, 134, 164 could be = used as=20 would occur to those skilled in the art. Generally, the optical filter = is=20 matched to the detected optical characteristic of the sensing matrix 50, = 150 and=20 light spectrum emitted by RL source 30, 130. The solid diagonal lines = used to=20 portray items 30, 36, 50, 60, 130, 150, and 154 are not intended to = indicate a=20 specific type of material, but rather generally depict a cross-sectional = view.=20

Besides a sensing matrix with Ru(dpp).sub.3 in PVC, tris(1,=20 10-phenanthroline) ruthenium (II) chloride (Ru(phen).sub.3) immobilized = in a=20 silicone substance also provides a sensing matrix suitable to detect = oxygen when=20 energized by an RL source. Other ruthenium complexes may also be used. = For=20 example, ruthenium complex matrices including, but not limited to:=20 (1)Ru(dpp).sub.3 in polystyrene, Ru(dpp).sub.3 in sol-gel, and = ruthenium-tris=20 (dipyridyl)-dichloride in silicone may be used as suitable fluorophores. = In=20 addition, polycyclic aromatic hydrocarbons (PAHs) in a glass support and = PAHs in=20 a polymer may be used in a fluorescence quenching type oxygen sensor = powered by=20 an RL source. The previously cited publications mention other compounds = as well=20 which could also be used as a fluorophore to be stimulated by light from = an RL=20 source in an optical sensor. Generally, these flourophores may be used = in=20 accordance with the present invention with conventional modifications to = optical=20 filters and phosphors as are known to those skilled in the art. =

It is to=20 be appreciated that in accordance with the present invention, a variety = of=20 biosensors can be constructed to monitor biochemical reactions. Such a = biosensor=20 may be made, for example, by coupling an oxygen sensor of the present = invention=20 to an appropriate oxydase enzyme or yeast. Such biosensors could be used = to=20 sense a wide variety of biological substances and reactions, including=20 cholesterol, glutamate, glucose, lactate, and biological oxygen demand.=20 Biosensing techniques which could incorporate a sensing mechanism of the = present=20 invention are described in the following publications: Baker and Gough, = A=20 Continuous, Implantable Lactate Sensor, 67 ANAL. CHEM. 1536-52 (1995); = Li and=20 Walt, 67 ANAL. CHEM. 3746-52 (1995); Preininger, Klimant and Wolfbeis, = Optical=20 Fiber Sensor for Biological Oxygen Demand, 66 ANAL. CHEM. 1841-46 = (1994); and=20 Moreno-Bondi, Wolfbeis, Leiner and Schaffar, Oxygen Optrode for Use in a = Fiber-Optic Glucose Biosensor, 62 ANAL. CHEM. 2377-80 (1990). =

Also, it=20 is to be appreciated that optical sensors of the present invention can = be=20 constructed to detect a variety of substances in addition to oxygen. For = one=20 embodiment, an optical sensor useful to detect CO.sub.2 may be energized = by=20 light from an RL source. The sensing matrix for this sensor includes a=20 luminophore portion which displays a change in color based on the = concentration=20 of CO.sub.2. As a result, a variable absorption of light form the RL = source=20 provides a variable light intensity level suitable for detection by a=20 photodetector. Similarly, a sensor to detect solution pH may be = constructed=20 using a properly selected RL source and sensing matrix configured with a = luminophore portion. Table 1 provides a listing of examples of matching=20 constituents of RL light sources, luminophores, and preferred matrix = fillers for=20 O.sub.2, CO.sub.2, and pH sensing mechanisms.

TABLE 1=20 ______________________________________ Sensor RL source Luminophore = Filler=20 ______________________________________ O.sub.2 ZnS:Ag and ruthenium = silicon/PVC/=20 .sup.147 Pm complexes polystyrene CO.sub.2 Y.sub.3 (Al, Ga).sub.5 = m-cresol ethyl=20 cellulose O.sub.12 :Ce purple and .sup.147 Pm pH Y.sub.2 O.sub.2 S:Eu = Merck N9=20 cellulose and .sup.147 Pm triacetate = ______________________________________=20

Besides .sup.147 Pm, other radioactive isotopes may be selected = which=20 are suitable for the RL source including .sup.3 H and .sup.14 C. In = addition,=20 the previously cited publications provide further examples of = luminophore-based=20 optical sensors which may be adapted for use with a self-powered light = source in=20 accordance with the present invention.

EXPERIMENTAL SECTION =

The=20 following examples are provided to further describe the objects, = features, and=20 advantages of the present invention, the same is to be considered as=20 illustrative and not restrictive or limiting in character. =

Example 1=20

In one experiment, a self-powered optical sensor was constructed = in=20 accordance with the present invention using an RL source. The RL source = included=20 20 uCi of .sup.14 C as the radioactive isotope in a .sup.14 C-hexadecane = radioactive constituent. The phosphor constituent of the RL source = included 0.05=20 gram of ZnS:Ag. The RL source provided a source of blue light. The = luminophore=20 was a ruthenium complex of tris(1,10-phenanthroline) ruthenium (II) = chloride=20 (Ru(phen).sub.3). The Ru(phen).sub.3 flourophore was immobilized in a = silicone=20 compound in the form of a membrane to provide the sensing matrix. =

The=20 sensor was constructed by enclosing the RL source in the bottom of a = glass vial=20 and fixing an epoxy plug over it. A plastic lid was used to seal the top = of the=20 vial. The sensing membrane was attached to the bottom of the glass vial = adjacent=20 a space configured for a flow through sample. The sensing membrane and = container=20 were spaced apart from the surface of a photomultiplier tube to define = the=20 sample space. Distinct signal changes were observed when the sample = space was=20 alternatively filled with pure nitrogen and oxygen.

Example 2 =

In=20 another experiment, the RL source was constructed in the following = manner. In a=20 3.4.times.0.7 cm outer diameter glass vial, 15.2 milligrams of the = phosphor=20 constituent ZnS:Ag was completely mixed with 110.3 microliters of 1 = molar NaOH,=20 then 94.3 microliters of .sup.147 PMCl.sub.3 solution (activity=3D0.5 = mCi) was=20 added to serve as the radioactive constituent. After the vial was = air-dried in a=20 fume hood for 4 days, the dry residue was covered by 0.8 milliliters of = epoxy=20 (epo-tek 301, Epoxy Technology Inc.) and oven-cured for 1 hour at = 65.degree. C.=20 The vial was then covered with a plastic lid, sealed with a thick layer = of=20 epoxy, and oven-cured for 1 hour at 65.degree. C. The glow from the = radioactive=20 ZNS:Ag layer was visible to the eye in darkness.=20 Tris(4,7-diphenyl-1,10-phenanthroline) ruthenium (II) chloride = (Ru(dpp).sub.3)=20 was immobilized in a layer of PVC. The resulting membrane was dip-coated = on the=20 outer surface of the vial to provide a sensing matrix. The components of = the=20 polymer solution for preparing the PVC membrane were 10 milliliters=20 tetrahydrofuran (THF), 1.5 milliliters methanol, 1 gram PVC, 40.5 = milligrams=20 Ru(dpp).sub.3 and 5 milliliters 2-nitrophenyl octyl ether.

FIG. = 3 shows=20 the response of the oxygen sensor to alternating nitrogen and oxygen = exposure=20 using the detection optics of a SLM AMINCO SPF-500C spectrofluorometer = to=20 monitor the Ru(dpp).sub.3 fluorescence. A calibration curve for this = novel=20 oxygen sensor is shown as a conventional Stern-Volmer plot in FIG. 4. = Important=20 sensor characteristics are:

1. Detection limit: 3.4 torr (0.45%) = O.sub.2=20 ;

2. Dynamic range: 3.4.about.760 torr; and

3. 95% = response=20 time: 12.5 .+-. 0.6 seconds.

The downward curvature of the = calibration=20 curve in FIG. 4 was improved by placing a blue optical filter between = the RL=20 source and the sensing matrix. FIG. 5 depicts the improved calibration = curve as=20 a comparison with FIG. 4 demonstrates.

All publications, = patents, and=20 patent applications cited in this specification are herein incorporated = by=20 reference as if each individual publication, patent, or patent = application were=20 specifically and individually indicated to be incorporated by reference. =

While the invention has been illustrated and described in detail = in the=20 drawings and foregoing description, the same is to be considered as = illustrative=20 and not restrictive in character, it being understood that only the = preferred=20 embodiment has been shown and described and that all changes and = modifications=20 that come within the spirit of the invention are desired to be = protected.=20

* * * * *
=20
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