US5498875A
Expired / Lapsed
US
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Signal processing for chemical analysis of samples
Assignee: Beckman Coulter Inc
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Filing: 1994-08-17
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Granted: 1996-03-12
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Expires: 2014-08-17
Abstract
Abstract A method and apparatus determines the analyte content of a sample by generating first and second input signals and directing the input signals to the sample. The input signals differ in wavelength by at least 3 nanometers. Due to the interaction between the input signals and the sample, first and second output signals are generated. Each output signal comprises a resonant signal whose peak wavelength is substantially independent of the wavelength of the respective input signal, and a non-resonant output signal whose peak wavelength is dependent upon the wavelength of respective input signal. A detector is used to detect the two output signals, and by distinguishing the resonant output signals from the non-resonant output signals, data about the analyte content of the sample is determined. Principal components regression analysis or multivariate quantitative analysis can be applied to the output signals, for the purpose of distinguishing between the resonant and non-resonant signals. The method and apparatus can also distinguish resonant output signals from each other, and non-resonant output signals from each other.
Inventors
- 👤 Robert J. Obremski
- 👤 John W. Silzel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 21:31
CPC Classifications
G; G01; G01N; G01N21/00; G01N21/17; G01N21/25; G01N21/31; G01N21/314; G01J; G01J3/00; G01J3/28; G01J3/42; G01J3/433; G01J3/4338; G01N21/62; G01N21/63; G01N21/64; G01N2201/00; G01N2201/12; G01N2201/129; G01N2201/1293
Claims Analysis
Total Claims: 55
Claim 1
Independent Claim
212 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal and (ii) a first non-resonant output signal whose peak wavelength is dependent upon the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal; (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the resonant output signals from the non-resonant output signals to obtain data about the analyte content of the sample.
Claim 2
Dependent Claim
212 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal and (ii) a first non-resonant output signal whose peak wavelength is dependent upon the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal; (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the resonant output signals from the non-resonant output signals to obtain data about the analyte content of the sample.
Claim 3
Dependent Claim
50 words
An apparatus as claimed in claim 1 wherein the signal generator comprises: (i) two separate sources, each one for generating a source signal; (ii) a modulator for selectively directing the source signals to the sample as the input signals; and (iii) means for directing the source signals to the modulator.
Claim 4
Dependent Claim
16 words
Apparatus as claimed in claim 2 wherein the sources are laser diodes operative at different wavelengths.
Claim 5
Dependent Claim
57 words
An apparatus as claimed in claim 2 wherein the modulator comprises a wavelength modulating device and the means for directing the first and second input signals comprises a fiberoptic waveguide having a common waveguide and two limbs, each limb being directed to one of the sources, with the common waveguide being directed to the wavelength modulating device.
Claim 6
Dependent Claim
16 words
Apparatus as claimed in claim 4 wherein the wavelength modulating device is a liquid crystal filter.
Claim 7
Dependent Claim
29 words
Apparatus as claimed in claim 1 including processing means between the sample and the detector, the processing means including at least one of a filter, dispersing element and monochromator.
Claim 8
Dependent Claim
19 words
Apparatus as claimed in claim 6 wherein the processing means includes the filter, the dispersing element and the monochromator.
Claim 9
Dependent Claim
27 words
Apparatus as claimed in claim 1 wherein the resonant output signals are signals responsive to molecular emission, including at least one of a fluorescence or phosphorescence signal.
Claim 10
Dependent Claim
24 words
Apparatus as claimed in claim 1 wherein the non-resonant signals include at least one of a Rayleigh signal, Mie, Brillouin, and Raman scattering signal.
Claim 11
Dependent Claim
27 words
Apparatus as claimed in claim 1 wherein the signal generator generates input signals such that the first and second resonant output signals have substantially the same spectra.
Claim 12
Dependent Claim
24 words
Apparatus as claimed in claim 10 wherein the signal generator further comprises means for generating the first and the second input signals in sequence.
Claim 13
Dependent Claim
49 words
Apparatus as claimed in claim 1 wherein the means for distinguishing the output signals comprises means for expressing the first and the second resonant output signals as a single eigenvector, wherein the first and the second non-resonant output signals are not capable of being expressed as a single eigenvector.
Claim 14
Dependent Claim
33 words
Apparatus as claimed in claim 1 wherein the means for distinguishing the output signals comprises means for selecting a predetermined number of eigenvectors for expressing the first and the second resonant output signals.
Claim 15
Dependent Claim
36 words
Apparatus as claimed in claim 1 wherein the distinguishing means comprises means for applying principal components regression analysis to the first second output signals, whereby the resonant output signals are distinguished from the non-resonant output signals.
Claim 16
Dependent Claim
44 words
Apparatus as claimed in claim 1 wherein the distinguishing means comprises means for applying multivariate quantitative analysis to the first and second output signals, whereby the first and the second resonant output signals are distinguished from the first and the second non-resonant output signals.
Claim 17
Dependent Claim
23 words
Apparatus as claimed in claim 15 wherein the first and second input wavelengths are separated by about 3 nanometers to about 40 nanometers.
Claim 18
Dependent Claim
122 words
Apparatus as claimed in claim 14 wherein the first resonant output signal and the second resonant output signal have a first spectrum and a second spectrum respectively, and wherein the first non-resonant output signal and the second non-resonant output signal have a third spectrum and a fourth spectrum respectively, and wherein the signal generator generates input signals such that the first and the second spectra are substantially the same, and such that the third and the fourth spectra are different, and wherein the means for principal components regression analysis comprises (i) means for retaining the first and the second resonant output signals having the same spectra and (ii) means for rejecting the first and the second non-resonant output signals having different spectra.
Claim 19
Dependent Claim
65 words
Apparatus as claimed in claim 1 wherein the analyte has an absorption level, and wherein the generator has one or more power levels, and wherein the generator further comprises means for selecting the first and the second wavelengths such that the mathematical product of the generator power level and the analyte absorption level is the same at the first and at the second wavelengths respectively.
Claim 20
Dependent Claim
99 words
Apparatus as claimed in claim 1 wherein the signal generator generates the first and the second input signals in sequence, and wherein the first and the second non-resonant output signals comprise first and second Raman signals respectively, the first and the second Raman signals having a first and a second Raman spectrum respectively, and wherein the first Raman spectrum is at a first spectral position dependent on the first wavelength, and the second Raman spectrum is at a second spectral position dependent on the second wavelength, and wherein the first spectral position is different from the second spectral position.
Claim 21
Dependent Claim
100 words
Apparatus as claimed in claim 1 wherein the signal generator generates the first and the second input signals in sequence, and wherein the first and the second non-resonant output signals comprise first and second Rayleigh scattering signals respectively, the first and the second Rayleigh signals having a first and a second Rayleigh spectrum respectively, and wherein the first Rayleigh spectrum is at a first spectral position dependent on the first wavelength, and the second Rayleigh spectrum is at a second spectral position dependent on the second wavelength, and wherein the first spectral position is different from the second spectral position.
Claim 22
Dependent Claim
215 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the first resonant output signal from the second resonant output signal to obtain data about the analyte content of the sample.
Claim 23
Dependent Claim
215 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the first resonant output signal from the second resonant output signal to obtain data about the analyte content of the sample.
Claim 24
Dependent Claim
89 words
Apparatus as claimed in claim 21 wherein the first resonant signal has a first spectrum comprising first and second component spectral curves, and wherein the second resonant signal has a second spectrum comprising a third and fourth component spectral curves, wherein the first and the third component spectral curves are related, and wherein the second and the fourth component spectral curves are related, and wherein the distinguishing means comprises means for distinguishing the first and the third related spectral curves from the second and the fourth related spectral curves.
Claim 25
Dependent Claim
27 words
Apparatus as claimed in claim 21 wherein the resonant output signals are signals responsive to molecular emission, including at least one of a fluorescence or phosphorescence signal.
Claim 26
Dependent Claim
25 words
Apparatus as claimed in claim 21 wherein the non-resonant output signals include at least one of a Rayleigh signal, Mie, Brillouin, and Raman scattering signal.
Claim 27
Dependent Claim
215 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the first non-resonant output signal from the second non-resonant output signal to obtain data about the analyte content of the sample.
Claim 28
Dependent Claim
215 words
Apparatus for determining the analyte content of a sample, the apparatus comprising: (a) a signal generator for generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) a means for directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) a detector for detecting the first and second output signals; and (d) means for distinguishing the first non-resonant output signal from the second non-resonant output signal to obtain data about the analyte content of the sample.
Claim 29
Dependent Claim
48 words
Apparatus as claimed in claim 25 wherein the first non-resonant output signal has a first spectrum and the second non-resonant output signal has a second spectrum, wherein the first and the second spectra are unrelated, and wherein the distinguishing means comprises means for distinguishing between the unrelated spectra.
Claim 30
Independent Claim
205 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal and (ii) a first non-resonant output signal whose peak wavelength is dependent upon the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal; (c) detecting the first and the second output signals; and (d) distinguishing the resonant output signals from the non-resonant output signals to obtain data about the analyte content of the sample.
Claim 31
Independent Claim
205 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal and (ii) a first non-resonant output signal whose peak wavelength is dependent upon the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal; (c) detecting the first and the second output signals; and (d) distinguishing the resonant output signals from the non-resonant output signals to obtain data about the analyte content of the sample.
Claim 32
Dependent Claim
51 words
The method of claim 27 wherein the step of generating the first and the second input signals comprises: (i) generating the signals from two separate sources, each one for generating a source signal, and (ii) modulating the source signals for selectively directing the source signals to the sample as input signals.
Claim 33
Dependent Claim
15 words
The method of claim 28 wherein the sources comprise laser diodes operating at different wavelengths.
Claim 34
Dependent Claim
66 words
The method of claim 28 wherein the step of modulating the source signals comprises modulating the signals using a wavelength modulating device, and wherein the step of directing the source signals comprises guiding the signals via a fiberoptic waveguide having a common waveguide and two limbs, each limb being directed to one of the sources, and the common waveguide being directed to the wavelength modulating device.
Claim 35
Dependent Claim
22 words
The method of claim 30 wherein the step of modulating the generated signals comprises modulating the signals by a liquid crystal filter.
Claim 36
Dependent Claim
23 words
The method of claim 27 comprising the additional step of filtering the output signals immediately before the step of detecting the output signals.
Claim 37
Dependent Claim
26 words
The method of claim 27 wherein the resonant output signals are signals responsive to molecular emission, including at least one of a fluorescence or phosphorescence signal.
Claim 38
Dependent Claim
23 words
The method of claim 27 wherein the non-resonant signals include at least one of a Rayleigh signal, Mie, Brillouin, and Raman scattering signal.
Claim 39
Dependent Claim
32 words
The method of claim 27 wherein the step of generating the input signals comprises generating the input signals such that the first and second resonant output signals have substantially the same spectra.
Claim 40
Dependent Claim
46 words
The method of claim 27 wherein the step of distinguishing the output signals comprises expressing the first and the second resonant output signals as a single eigenvector, wherein the first and the second non-resonant output signals are not capable of being expressed as a single eigenvector.
Claim 41
Dependent Claim
30 words
The method of claim 27 wherein the step of distinguishing the output signals comprises selecting a predetermined number of eigenvectors for expressing the first and the second resonant output signals.
Claim 42
Dependent Claim
39 words
The method of claim 27 wherein the step of distinguishing the output signals comprises applying principal components regression analysis to the first output and second output signals, whereby the resonant output signals are distinguished from the non-resonant output signals.
Claim 43
Dependent Claim
47 words
The method of claim 27 wherein the step of distinguishing the output signals comprises applying a multivariate quantitative analysis to the first and the second output signals, whereby the first and the second resonant output signals are distinguished from the first and the second non-resonant output signals.
Claim 44
Dependent Claim
35 words
The method of claim 39 wherein the step of generating the input signals comprises generating the signals such that the first and the second wavelengths are separated by about 3 nanometers to about 40 nanometers.
Claim 45
Dependent Claim
119 words
The method of claim 38 wherein the first and the second resonant output signals have a first and a second spectrum respectively, and wherein the first and the second non-resonant output signals have a third and a fourth spectrum respectively, and wherein the step of generating the input signals comprises selecting the first and the second wavelengths such that the first and the second spectra are substantially the same, and such that the third and the fourth spectra are different, and wherein the step of applying principal components regression analysis comprises (i) retaining the first and the second resonant output signals having the same spectra and (ii) rejecting the first and the second non-resonant output signals having different spectra.
Claim 46
Dependent Claim
103 words
The method of claim 27 wherein the step of generating the input signals comprises generating the first and the second input signals in sequence, and wherein the first and the second non-resonant output signals comprise first and second Raman signals respectively, the first and the second Raman signals having a first and a second Raman spectrum respectively, and wherein the first Raman spectrum is at a first spectral position dependent on the first wavelength, and the second Raman spectrum is at a second spectral position dependent on the second wavelength, and wherein the first spectral position is different from the second spectral position.
Claim 47
Dependent Claim
104 words
The method of claim 27 wherein the step of generating the input signals comprises generating the first and the second input signals in sequence, and wherein the first and the second non-resonant output signals comprise first and second Rayleigh scattering signals respectively, the first and the second Rayleigh signals having a first and a second Rayleigh spectrum respectively, and wherein the first Rayleigh spectrum is at a first spectral position dependent on the first wavelength, and the second Rayleigh spectrum is at a second spectral position dependent on the second wavelength, and wherein the first spectral position is different from the second spectral position.
Claim 48
Independent Claim
207 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) detecting the first and second output signals; and (d) distinguishing the first resonant output signal from the second resonant output signal to obtain data about the analyte content of the sample.
Claim 49
Independent Claim
207 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) detecting the first and second output signals; and (d) distinguishing the first resonant output signal from the second resonant output signal to obtain data about the analyte content of the sample.
Claim 50
Dependent Claim
91 words
The method of claim 44 wherein the first resonant output signal has a first spectrum comprising first and second component spectral curves, and wherein the second resonant output signal has a second spectrum comprising third and fourth component spectral curves, wherein the first and the third component spectral curves are related, and wherein the second and the fourth component spectral curves are related, and wherein the step of distinguishing the output signals comprises distinguishing the first and the third related spectral curves from the second and the fourth related spectral curves.
Claim 51
Dependent Claim
26 words
The method of claim 44 wherein the resonant output signals are signals responsive to molecular emission, including at least one of a fluorescence or phosphorescence signal.
Claim 52
Dependent Claim
23 words
The method of claim 44 wherein the non-resonant signals include at least one of a Rayleigh signal, Mie, Brillouin, and Raman scattering signal.
Claim 53
Independent Claim
207 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) detecting the first and second output signals; and (d) distinguishing the first non-resonant output signal from the second non-resonant output signal to obtain data about the analyte content of the sample.
Claim 54
Independent Claim
207 words
A method for determining the analyte content of a sample, the method comprising the steps of: (a) generating a first input signal having a first wavelength, and a second input signal having a second wavelength, the two wavelengths differing by at least about 3 nanometers; (b) directing the first and second input signals to a sample containing an analyte to generate, respectively, a first output signal and a second output signal due to interactions between the input signals and the analyte, wherein the first output signal comprises: (i) a first resonant output signal whose peak wavelength is substantially independent of the wavelength of the first input signal, and (ii) a first non-resonant output signal whose peak wavelength is dependent on the wavelength of the first input signal, and wherein the second output signal comprises: (i) a second resonant output signal whose peak wavelength is substantially independent of the wavelength of the second input signal, and (ii) a second non-resonant output signal whose peak wavelength is dependent on the wavelength of the second input signal, and (c) detecting the first and second output signals; and (d) distinguishing the first non-resonant output signal from the second non-resonant output signal to obtain data about the analyte content of the sample.
Claim 55
Dependent Claim
47 words
The method of claim 48 wherein the first non-resonant signal has a first spectrum and the second non-resonant signal has a second spectrum, wherein the first and the second spectra are unrelated, and wherein the step of distinguishing the output signals comprises distinguishing between the unrelated spectra.
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