U.S. patent number 3,717,412 [Application Number 05/092,979] was granted by the patent office on 1973-02-20 for method for analyzing spectral data using halograms.
This patent grant is currently assigned to Nihon Denski Kabushiki Kaisha. Invention is credited to Koji Masutani, Hajime Mori, Hiroshi Takuma, Kazuko Umezu.
United States Patent |
3,717,412 |
Takuma , et al. |
February 20, 1973 |
METHOD FOR ANALYZING SPECTRAL DATA USING HALOGRAMS
Abstract
A signal obtained by an analytical instrument is converted into
a light and shade spectrum by an electron exposure unit, the said
light and shade spectrum then being formed into a hologram. Unknown
samples are qualitatively and quantitatively analyzed by
correlating the hologram formed by a given unknown sample with the
hologram of a known sample. Further, if the output signal from an
interference spectrometer is fed into the exposure unit, a light
and shade spectrum in the form of a hologram is produced. By
applying Fraunhofer diffraction, Fourier transformed spectrum in
reverse corresponding to a wave number is derived from the said
hologram.
Inventors: |
Takuma; Hiroshi (Tokyo,
JA), Mori; Hajime (Tokyo, JA), Masutani;
Koji (Tokyo, JA), Umezu; Kazuko (Yokohama,
JA) |
Assignee: |
Nihon Denski Kabushiki Kaisha
(Tokyo, JA)
|
Family
ID: |
26437113 |
Appl.
No.: |
05/092,979 |
Filed: |
November 27, 1970 |
Foreign Application Priority Data
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|
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Nov 28, 1969 [JA] |
|
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44/95946 |
Nov 28, 1969 [JA] |
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44/95947 |
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Current U.S.
Class: |
356/300; 250/395;
356/303; 359/9; 356/457; 356/451; 250/282; 356/71; 359/32;
346/107.1 |
Current CPC
Class: |
G01R
33/28 (20130101); G01N 30/8651 (20130101); G01J
3/453 (20130101); G06E 3/001 (20130101) |
Current International
Class: |
G01N
30/00 (20060101); G01J 3/45 (20060101); G01N
30/86 (20060101); G01J 3/453 (20060101); G01R
33/28 (20060101); G06E 3/00 (20060101); G01j
003/40 (); G01b 009/02 (); G01k 009/08 () |
Field of
Search: |
;350/162SF
;356/71,74,77,16S ;250/65R,65F |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Moire Pattern Resulting From Superposition of Two Zone Plates";
Chau; Applied Optics; Vol. 8 No. 8; Aug. 69 pg. 1707-1712..
|
Primary Examiner: Wibert; Ronald L.
Assistant Examiner: McGraw; V. P.
Claims
Having thus described the invention with the detail and
particularity as required by the Patent Laws, what is desired
protected by Letters Patent is set forth in the following
claims:
1. A method of analyzing spectral data received from an analytical
instrument which produces the information signal from a sample
comprising the steps for:
A. converting the information signal into a one-dimensional
spectrum;
B. forming a hologram of said one-dimensional spectrum;
C. juxtaposing the hologram of step B with holograms of known
samples and passing light therethrough;
D. observing the light passed therethrough to correlate the
spectrum of the sample with the known samples.
Description
This invention relates to a method and apparatus for processing
data in an analytical instrument. More particularly, this invention
relates to a method and apparatus for processing the data obtained
from an analytical instrument into data from which the spectral
pattern of the specimen can be discerned.
Generally, data provided by an analytical instrument is recorded on
chart paper as a two-dimensional spectrum. For example, in the case
of nuclear magnetic resonance apparatus, the abscissa of the
recorded spectrum represents the swept high frequency and the
ordinate represents the signal intensity. The spectrum thus
obtained contains micro-information pertaining to the sample, the
said information being analyzed by comparing the said spectrum with
the spectrum of a known sample. The comparison is usually entrusted
to the judgment of the research worker involved with the result
that when the spectrum of the known sample and the spectrum of the
unknown sample have similar peaks, it is difficult to make a
precise comparison. Again, this method is extremely time consuming
inasmuch as the unknown spectrum has to be compared with the
spectra of a large number of known samples.
Another method of data processing is to use an interference
spectrometer. In this case, a ray of light generated by a light
source is split into two rays of light, one ray being reflected by
a movable reflector, the other by a fixed reflector. The two light
rays are then unified by the beam splitter. As a result, the
increase or decrease of the light intensity is determined by the
interference of the two light rays and detected by a detector.
Further, by scanning the said movable reflector, the variation of
the interference pattern, determined by the difference in the
optical path, is also detected. Advantages claimed for this type of
spectrometer are high S/N (signal to noise) ratio and short
measuring time. Disadvantages, however, as in the case of the
aforegoing, include time consuming data processing, caused by the
fact that the detected spectrum is a Fourier transformed spectrum
of the light generated by the light source.
In accordance with this invention, the output signal from any one
of a number of types of analytical instrument is converted into a
one-dimensional spectrum such as a light and shade or uneven
spectrum. Subsequently, a hologram of such a spectrum is formed and
the pattern is discerned by correlation. Correlation is carried out
by fixing two holograms together and irradiating them with a laser
beam. By so doing, the spectrum obtained by the analytical
instrument is automatically analyzed both speedily and easily. It
should be mentioned here, however, that since the patterns of any
two two-dimensional spectra are different due to the difference in
sample quantity and density, it is impossible to discern the
hologram pattern by correlating the said two two-dimensional
spectra.
Again, in accordance with this invention, the output signal from an
interference spectrometer is similarly converted into a
one-dimensional spectrum such as a light and shade or uneven
spectrum, the said spectrum serving as a hologram. Pattern
discernment is also effected by correlation. Since, in this case,
the hologram is reversely Fourier transformed by Fraunhofer
diffraction, the data obtained from the interference spectrometer
is optically analyzed both speedily and easily.
One object of this invention is to provide a method and apparatus
for processing data optically in an analytical instrument.
Another object of this invention is to provide a method and
apparatus for processing data rapidly in an analytical
instrument.
Various other objects and advantages of this invention will become
apparent from the following detailed description made with
reference to the accompanying drawings in which:
FIG. 1 shows a nuclear magnetic resonance apparatus according to
this invention.
FIG. 2 shows an output signal wave form of the nuclear magnetic
resonance apparatus recorded on chart paper.
FIG. 3 shows a light and shade spectrum obtained by the apparatus
shown in FIG. 1.
FIG. 4 shows an optical system for producing a hologram.
FIG. 5 shows a optical system for correlating any two
holograms.
FIG. 6 shows another embodiment for producing a one dimensional
spectrum.
FIG. 7 shows a mass spectrometer according to this invention.
FIG. 8 shows a liquid chromatograph according to this
invention.
FIG. 9 shows a spectrometer according to this invention.
FIG. 10 shows an interference spectrometer according to this
invention.
FIG. 11 shows a light and shade spectrum produced by the
spectrometer shown in FIG. 10.
FIG. 12 shows an optical system for carrying out Fraunhofer
diffraction.
Referring to FIG. 1, a sample is enclosed in a probe 1, DC and high
frequency magnetic fields are produced around the said probe by an
electro-magnet 2 and a high frequency coil 3 to which a high
frequency is supplied by a sweep generator 4. By sweeping the high
frequency, high frequency energy is absorbed by the sample at
certain frequencies. The absorption signal is detected by a circuit
5 and a detector 6. FIG. 2 shows the output signal wave form of the
detector 6. Normally, the spectrum shown in FIG. 2 is obtained by
means of a recorder. According to this invention, however, the said
spectrum is converted into a light and shade or uneven spectrum by
feeding the output signal of the detector 6 into an electron beam
exposure unit 7.
An electron beam produced by a filament 8 is controlled by a grid 9
in circuit with the detector 6, accelerated by an anode 10, and
focused by an electron lens 11. The focused electron beam is
deflected by a deflecting coil 12 and irradiated on a movable plate
13 arranged on rollers 14 so that the electron beam is scanned at
right angles to the direction of plate movement. By so doing, a
light and shade spectrum as shown in FIG. 3 is recorded on the
plate 13 according to the intensity of the electron beam.
The said light and shade spectrum is then converted into a
hologram. FIG. 4 shows an embodiment for producing such a hologram.
In the figure, a laser beam generated by a laser 21 such as a He-Ne
laser is split into two beams by a beam splitter 22. One beam is
diffracted by a plate 23, on which the light and shade spectrum is
recorded, and then irradiated on a film plate 24. The other beam is
reflected by a reflector 25, bent by a prism 26 and then irradiated
on the said film plate 24. By so doing, the two beams form an
interference pattern, viz, a hologram which is recorded on the film
plate 24.
The recognition of the spectrum pattern obtained by the analytical
instrument can be effected by the hologram according to this
invention. Correlation of any tow holograms is effected by fixing
them together and irradiating a laser beam on the fixed holograms.
FIG. 5 shows the optical system for effecting the above
correlation. In the figure, a laser beam is irradiated on and
diffracted by the fixed holograms 31 and 32. The diffracted laser
beam is then focused on a screen 33 by a cylindrical lens 34. If
both holograms 31 and 32 have the same pattern, a light spectrum is
produced on the screen 33. Conversely, if their patterns are
different, the light spectrum does not appear on the screen.
Therefore, by using a hologram of an unknown sample as the hologram
31 and a hologram of a known sample as the hologram 32, the unknown
sample can be qualitatively analyzed.
It is also possible to quantitatively analyze the unknown sample.
The density of the interference pattern changes according to the
intensity of the output signal produced by the analytical
instrument. In the correlation, even if one hologram has the same
pattern as the other, the brightness of the spectrum on the screen
changes according to the difference in the densities of the two
holograms. This being so, the unknown sample can be quantitatively
analyzed by observing the spectrum brightness.
FIG. 6 shows another embodiment using an electro-optics element for
forming a light and shade or uneven spectrum. In the figure, a
monochromatic light generated by a light source 41 passes through
an electro-optics element 42, such as a KDP or ADP element, is
focused by a cylindrical lens 47 and then irradiated a silver
halide coated plate 43 which is moved by a motor 44. The output
voltage of a detector 6 is applied to electrodes 45 and 46. Thus,
the transmissivity of the light passing through the electro-optics
element varies according to the output voltage of the detector 6
with the result that a light and shade spectrum is recorded on the
plate 43. By coating the plate surface with photoresist instead of
silver halide, an uneven spectrum can be recorded on the plate.
FIG. 7 shows a mass spectrometer according to this invention. In
the figure, an ion beam emitted from an ion source 51 is
accelerated by acceleration slits 52 and then passes through a
magnetic field produced by an electro-magnet 53 to which an
excitation current is supplied by a variable power source 54. The
accelerated ion beam is dispersed according to the ion
mass-to-charge (m/e) ratio by the said magnetic field. Only ions
having a certain mass-to-charge ratio pass through a slit 55, the
said ions being detected by an ion collector 56. The output signal
of the collector 56 is fed into the electron beam exposure unit 7
via an amplifier 57. By varying the intensity of the magnetic field
produced by the electro-magnet 53, a light and shade or uneven
spectrum is recorded by the electron beam exposure unit. The said
spectrum is then converted into a hologram by the optical system
shown in FIG. 4.
FIG. 8 shows a liquid chromatograph according to this invention. An
eluant 61 in an eluant reservoir 62 is fed into a column 63,
containing a fixed phase 64 such as ion exchange resin, via a pipe
65 by a pump 66. A liquid sample is injected into the column 63 via
a sample inlet port 67 which is separated into its various
components according to the chromatograph phenomenon by the fixed
phase. The separated components are then detected by a detector 68,
and the eluant and liquid sample passed through the detector 68 is
collected in a reservoir 69. The signal detected by the detector 68
is fed into the electron beam exposure unit 7 via an amplifier 70
so as to record a one-dimensional spectrum.
FIG. 9 shows a spectrometer according to this invention. In the
figure, light from a light source (not shown) passes through an
inlet slit 81 into a monchromator 82. The light is reflected by a
reflector 83 and irradiated on a rotatable grating 84 so that the
irradiated light is dispersed in accordance with the wavelength.
The dispersed light is reflected by a reflector 85, passes through
an outlet slit 86 and is detected by a detector 87 such as a
photomultiplier. The detected electrical signal is fed into the
electron beam exposure unit 7 via an amplifier 88 so as to record a
one-dimensional spectrum such as a light and shade or uneven
spectrum.
FIG. 10 shows an interference spectrometer according to this
invention. In the figure, a light generated by a light source 91 is
made to form a parallel ray of light by a lens 92. The parallel
light is split into two rays of light by a beam splitter 93 so that
the split rays are directed to movable and fixed mirrors 94 and 95
respectively. The said movable mirror 94 is moved at a constant
speed by a motor 96. The light reflected by the movable mirror 94
passes through the beam splitter 93 and is focused on a detector 97
by a lens 98. The amplitude Fa (.nu.) of this light is expressed as
follows:
Fa (.nu.) .varies. A (.nu.) cos 2.pi.(ft - 21.nu.)
where A(.nu.) is the amplitude of the light generated by the light
source 91, f is the light frequency, .nu. is the wave number (i.e.,
reciprocal of wave length) of the light and l is the distance
between the beam splitter 93 and the movable mirror 94.
On the other hand, the amplitude Fb (.nu.) of the light reflected
by the fixed mirror 95, which is similarly reflected by the beam
splitter 93 and focused on the detector 97 by the lens 98, is
expressed as follows:
Fb (.nu.) .varies. A (.nu.)cos 2 .pi.[ft- 2 (l +.DELTA.) .nu.]
where .DELTA. is half the optical path difference between the two
rays of light.
The said two rays of light cause an interference phenomenon to
occur on the detector screen, the amplitude F (.DELTA.) of the
detected light being expressed as follows: ##SPC1##
Further, the energy intensity of the light is equal to F.sup.2
(.DELTA.) and is expressed as follows:
Since I (.DELTA.) is proportional to the squared average value of
the optical disturbance, the time factor included in the amplitude
F (.DELTA.) disappears.
I (.DELTA.) is represented as an interferogram which is a Fourier
transformed spectrum of the energy intensity of the light generated
by the light source. A spectrum corresponding to the wave number is
obtained by carrying out the Fourier transformation of I (.DELTA.)
in reverse. Normally, I (.DELTA.) is transformed by an electronic
computer by which means transformation is extremely complicated and
elaborate. Optical transformation, on the other hand, as effected
by this invention, simplifies the process appreciably.
The signal detected by the detector 97 is amplified by an amplifier
99 and fed into the electron beam exposure unit 7. The resultant
light and shade spectrum as shown in FIG. 11 is then recorded on
the plate 100, the information intensity contained thereon being
expressed as follows:
where .gamma. is the gradient of the linear part of the plate
transfer curve and x is defined by the relation 2 .DELTA./M where M
is a constant.
Further, since the light and shade spectrum recorded on the plate
100 represents the interference pattern, that is to say, the
hologram formed by the two rays of light, the reverse Fourier
transformed spectrum can be obtained therefrom by Fraunhofer
diffraction. FIG. 12 shows the optical system of this said
diffraction. Here, a monochromatic light 101, such as a laser
light, is irradiated on the plate 100 where the light and shade
spectrum is recorded and diffracted. The diffracted light is then
focused on a screen 102 by a cylindrical lens 103.
In this system, the amplitude T(x) of the diffracted light is
expressed as follows: ##SPC2##
Now, according to Fraunhofer's diffraction theory, the amplitude D
(.xi.) of the spectrum projected on the screen 102 is given as
follows: ##SPC3##
where .xi. is the distance from the screen center 0, R is a
constant defined by the relation 2 .pi. .nu.'/f, is the wave number
of the incident light 101 and is the focal length of the
cylindrical lens 103, thus, the energy intensity I (.xi.) of the
light projected on the screen is equal to D.sup.2 (.xi.) and is
expressed as follows:
In the above relationship, the first term expresses the zero order
transmission diffracted light, the second term expresses the +1
order diffracted light and the third term expresses the -1 order
diffracted light. Considering the +1 order diffracted light,
when
light possessing energy .pi..sup.2 .nu..sup.2 A.sup.4 (.nu.) is
projected on the screen 102. As a result, when a light spot is
projected on a point which is at a distance d from the center 0,
the wave number of the light spot spectrum is calculated by the
following relationship:
.nu. =d .nu.'/M f'
Consequently, the entire spectrum is obtained by calculating the
wave number of each light spot spectrum appearing on the screen.
Since, however, the diffracted light rays of the +1 and -1 order
diffracted light are symmetrical, it is sufficient to calculate one
order only. In addition, the spectrum pattern can be discerned by
means of a hologram by using the optical system shown in FIG.
5.
* * * * *