JP5880164B2 - Fluorescence analyzer - Google Patents

Description

  The present invention relates to a fluorescence analyzer that obtains information about a component to be measured in a sample by fluorescence emitted from the sample. More specifically, the present invention relates to a fluorescence analyzer that can easily check and update the reliability of calibration data.

By measuring fluorescence (including intensity and quenching time) emitted from a measurement target component in the sample, a reaction product with the measurement target component, or a reagent that reacts with the measurement target component, Fluorescence analysis that measures concentration is widely used.
A fluorescence analyzer that performs fluorescence analysis stores calibration data (a calibration curve or the like) that correlates a detection value of a fluorescence detector and a measurement target component in a sample, and thereby determines a measurement target component from the detection value of the fluorescence detector. Information can be obtained.

  In recent fluorescence analyzers, both the amount of excitation light and the sensitivity of the fluorescence detector change little over time, and the calibration data once stored can be used to some extent continuously. However, there may be a slight sensitivity shift over time due to contamination of the optical system that guides excitation light or fluorescence. In some cases, the detection value greatly deviates from the detection value that should be originally obtained due to some trouble such as deterioration of the excitation light source or the detector. For this reason, it is necessary to periodically perform calibration work for confirming the reliability of the calibration data and updating the calibration data.

Basically, the calibration data is created using a standard sample in which a predetermined reagent and a measurement target component amount are known. However, periodically performing a calibration operation using a reagent or a standard sample causes an increase in the running cost of the fluorescence analyzer.
In order to avoid complicated calibration work by humans, it is conceivable to automate the calibration work using a reagent or a standard sample. In this case, however, the entire apparatus becomes complicated and large. Furthermore, some reagents and the like are likely to deteriorate with time, and even if the calibration work using the reagents and the like is automated, it is likely to cause a problem if the calibration work is repeated for a long period of time.
Therefore, the present applicant has proposed to perform a calibration operation using a solid standard phosphor that emits constant fluorescence under a predetermined condition as a simple calibration method that does not use a reagent or the like (Patent Document 1). In Patent Document 1, a driving mechanism for moving the solid standard phosphor is provided, and the calibration is performed using the solid standard phosphor by arranging the solid standard phosphor at the position of the sample during calibration and retracting it after the calibration is completed. It is also proposed to automate.

JP 2004-157018 A

However, as disclosed in Patent Document 1, when a drive mechanism is provided to automate a calibration operation using a solid standard phosphor, the apparatus becomes large and complicated, and further, the presence of the drive mechanism tends to cause a failure. Produce. For this reason, automation of the calibration work using the solid standard phosphor is not worth the cost, and it has been selected that the person goes to the site where the fluorescence analyzer is located and performs the calibration work manually.
The present invention has been made in view of the above circumstances, and provides a fluorescence analyzer that can be easily calibrated without using a reagent or the like without complicating the apparatus and that can be automated. Let it be an issue.

In order to achieve the above object, the present invention employs the following configuration.
[1] An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence A fluorescence detection optical system that guides the sample from the sample to the fluorescence detector, a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector, and calibration optics that guides the calibration light from the calibration light source to the fluorescence detector Calibration data that correlates the system, the detection value of the fluorescence detector and the amount of the measurement target component in the sample, and the output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector Equipped with a converter
The optical path by the calibration optical system overlaps at least a part of the optical path by the fluorescence detection optical system,
The converter outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector and the calibration data when only the excitation light source is turned on, and turns on only the calibration light source. A fluorescence analyzer characterized by determining whether or not an alarm signal needs to be output based on a detection value of the fluorescence detector at the time, and outputting an alarm signal when it is determined that an alarm signal needs to be output.

[2] An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence A fluorescence detection optical system that guides the sample from the sample to the fluorescence detector, a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector, and calibration optics that guides the calibration light from the calibration light source to the fluorescence detector Calibration data that correlates the system, the detection value of the fluorescence detector and the amount of the measurement target component in the sample, and the output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector Equipped with a converter
The optical path by the calibration optical system overlaps at least a part of the optical path by the fluorescence detection optical system,
The converter outputs an output corresponding to the amount of the measurement target component in the sample based on the detection value of the fluorescence detector when only the excitation light source is turned on and the calibration data, and when only the calibration light source is turned on The fluorescence data is updated based on the detection value of the fluorescence detector.

[3] An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence A fluorescence detection optical system that guides the sample from the sample to the fluorescence detector, a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector, and calibration optics that guides the calibration light from the calibration light source to the fluorescence detector Calibration data that correlates the system, the detection value of the fluorescence detector and the amount of the measurement target component in the sample, and the output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector Equipped with a converter
The optical path by the calibration optical system overlaps at least a part of the optical path by the fluorescence detection optical system,
The converter outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector and the calibration data when only the excitation light source is turned on, and turns on only the calibration light source. Fluorescence analyzer characterized by determining whether or not calibration data needs to be updated based on the detection value of the fluorescence detector at the time, and updating the calibration data when it is determined that calibration data needs to be updated .

[4] The calibration optical system includes a calibration light irradiation optical system that guides the calibration light from the calibration light source to the sample, and calibration light detection optics that guides the calibration light scattered by the sample from the sample to the fluorescence detector. The fluorescence analysis apparatus according to any one of [1] to [3], in which the fluorescence detection optical system also serves as the calibration light detection optical system.
[5] The sample is a liquid,
Further, in order to obtain response light according to the disturbing component of the sample, a correction light source that emits a predetermined amount of correction light, a response light detector that detects response light emitted from the sample by the correction light, and A correction light irradiation optical system for guiding correction light to the sample, and a response light detection optical system for guiding the response light from the sample to the response light detector,
The converter is based on the detection value of the response light detector when only the correction light source is turned on, and the sample based on the detection value of the fluorescence detector and only the calibration data when only the excitation light source is turned on The fluorescence analyzer according to any one of [1] to [4], which corrects an output corresponding to a measurement target component amount.

[6] The sample is a liquid,
Further, in order to obtain response light according to the disturbing component of the sample, a correction light source that emits a predetermined amount of correction light, a response light detector that detects response light emitted from the sample by the correction light, and A correction light irradiation optical system for guiding correction light to the sample, and a response light detection optical system for guiding the response light from the sample to the response light detector,
The light emitting unit of the calibration light source and the light emitting unit of the correction light source are housed in a single package,
The calibration optical system includes a calibration light irradiation optical system that guides the calibration light from the calibration light source to the sample, and a calibration light detection optical system that guides the calibration light scattered by the sample from the sample to the fluorescence detector. Become
The calibration light irradiation optical system also serves as the correction light irradiation optical system,
The fluorescence detection optical system also serves as the calibration light detection optical system,
The converter is based on the detection value of the response light detector when only the correction light source is turned on, and the sample based on the detection value of the fluorescence detector and only the calibration data when only the excitation light source is turned on The fluorescence analyzer according to any one of [1] to [3], which corrects an output corresponding to the amount of the component to be measured.

  According to the fluorescence analyzer of the present invention, a simple calibration operation without using a reagent or the like can be performed without complicating the apparatus. Moreover, the calibration work can be automated.

1 is a schematic configuration diagram of a fluorescence analyzer according to an embodiment of the present invention. It is a schematic block diagram of the fluorescence analyzer which concerns on other embodiment of this invention.

<First Embodiment>
A fluorescence analyzer according to the first embodiment of the present invention will be described. As shown in FIG. 1, the fluorescence analyzer 1 of the present embodiment includes a sample unit 10, a detection unit 20, and a converter 40.
The sample unit 10 includes a light-shielding sample case 11 having an upper opening, a sample tank 12 disposed below the sample case 11 and shielded from light by the sample case 11, and a cylinder provided in the sample tank 12. 13. The cylindrical body 13 has a lower opening 13a at the lower end and an upper opening 13b that is substantially horizontal at the upper end. The sample tank 12 is provided with a sample water inlet 14 and a sample water outlet 15.

In the sample section 10, when sample water S (liquid sample) flows from the sample water inlet 14, the sample section 10 descends between the inner wall of the sample tank 12 and the outer periphery of the cylindrical body 13. The sample water S descending to the lower end of the cylinder 13 flows into the cylinder 13 from the lower opening 13a of the cylinder 13 and overflows from the substantially horizontal upper opening 13b on the upper end side of the cylinder 13. The overflow surface 17 is formed. The overflowed sample water S is guided to the sample water outlet 15 and discharged.
During the operation of the fluorescence analyzer 1, the inflow / outflow of the sample water S with respect to the sample unit 10 is always continued in principle, and the overflow surface 17 is always formed.

The detection unit 20 includes a light-shielding detection unit case 21 installed on the sample case 11, an excitation light source 22, a fluorescence detector 23, and a calibration light source 24 housed in the detection unit case 21.
A cell window 25 is provided on the lower surface wall of the detection unit case 21 and facing the overflow surface 17. The cell window 25 has a lens shape that converges the parallel light emitted from the detection unit 20 side to the sample unit 10 on the overflow surface 17 and uses the light incident on the detection unit 20 from the sample unit 10 side as parallel light. .

The excitation light source 22, Xe flash lamp (xenon discharge tube) can be used D ₂ lamp (deuterium discharge tube) or the like. A monochromatic light source such as a laser light source that emits light having a desired wavelength may be used. The excitation light source 22 is preferably one in which light amount feedback control is performed using a reference detector.
As the fluorescence detector 23, a photomultiplier tube, a photodiode, a phototransistor, an avalanche photodiode, or the like can be used as appropriate.
As the calibration light source 24, a light source that emits light that can be detected by a fluorescence detector with a predetermined light amount is used. The predetermined amount of light means that the amount of light is known. The predetermined light amount may be a fixed amount or a variable amount that can be appropriately selected by the converter 40.
The light emitted from the calibration light source 24 preferably includes light having the same wavelength as the fluorescence F emitted from the sample water S. The peak wavelength of the light emitted from the calibration light source 24 is preferably close to the wavelength of the fluorescence F emitted from the sample water S, and is particularly preferably the same.
It is preferable to use a light emitting diode as the calibration light source 24 because the amount of light is stable, inexpensive, and small.

The fluorescence detector 23 is disposed on a substantially vertical line of the cell window 25. A dichroic mirror 26 is disposed between the fluorescence detector 23 and the cell window 25, and the excitation light source 22 is disposed at substantially the same height as the dichroic mirror 26.
The dichroic mirror 26 reflects light of the wavelength of the excitation light E from the excitation light source 22 and transmits light of other wavelengths. The dichroic mirror 26 is disposed at an angle of 45 degrees with respect to the excitation light source 22 with the reflection surface facing downward. Has been.
The calibration light source 24 is arranged at the lower end of the detection unit case 21 so that the light emitting unit 24 a is below the fluorescence detector 23.

Further, on the emission side of the excitation light source 22, a lens 31 that makes the excitation light E from the excitation light source 22 parallel light and a wavelength selection filter 32 that narrows the wavelength of the excitation light E to a wavelength region suitable for excitation are sequentially arranged. ing. Note that when the excitation light source 22 is a light source that emits monochromatic light, the wavelength selection filter 32 is not necessary. Further, when the excitation light source 22 is a light source that emits parallel light, the lens 31 is not necessary.
Further, on the fluorescence detector 23 side of the dichroic mirror 26, a wavelength selection filter 34 that selectively transmits the fluorescence F emitted from the sample water S, and a lens 33 that integrates the parallel light from the dichroic mirror 26 in the fluorescence detector 23. Are arranged sequentially.

In the present embodiment, the excitation light irradiation optical system that guides the excitation light E from the excitation light source 22 to the overflow surface 17 of the sample water S is configured by the lens 31, the wavelength selection filter 32, the dichroic mirror 26, and the cell window 25. .
The fluorescence detection optical system that guides the fluorescence F emitted from the sample water S to the fluorescence detector 23 from the sample water S is constituted by the cell window 25, the dichroic mirror 26, the wavelength selection filter 34, and the lens 33.
A calibration optical system that guides the calibration light C from the calibration light source 24 to the fluorescence detector 23 includes a dichroic mirror 26, a wavelength selection filter 34, and a lens 33.
As shown in FIG. 1, the optical path by the calibration optical system of the present embodiment overlaps the optical path after the cell window 25 by the fluorescence detection optical system (the optical path from the upper side of the cell window 25 to the fluorescence detector 23). That is, the optical path by the calibration optical system of this embodiment overlaps with a part of the optical path by the fluorescence detection optical system.

The converter 40 stores calibration data that associates the detection value of the fluorescence detector 23 with the amount of the measurement target component in the sample water S. Here, the correlation between the detection value of the fluorescence detector 23 and the measurement target component amount may not be direct. For example, the amount of a reaction product with a measurement target component, the amount of a reagent that reacts with the measurement target component, and other component amounts that can be derived from the measurement target component amount and detection values corresponding to the measurement target component amount. , You may associate.
It is preferable that the initial value of the calibration data is created by initial calibration using a standard sample having a known reagent and a measurement target component amount after the fluorescence analyzer 1 is manufactured.
For example, when the calibration data specifies a calibration curve (y = a ₀ x) passing through the origin in the graph where the detection value of the fluorescence detector 23 is the x axis and the measurement target component amount is y, The initial calibration point is stored as initial calibration data. Thereby, a straight line passing through the initial calibration point and the origin can be specified as an initial calibration curve.
Initial calibration point:
x is the detection value of the fluorescence detector 23 in the initial calibration using the standard sample, and y is the measurement target component amount of the standard sample.

The converter 40 of this embodiment selects a measurement mode, a calibration mode, and other modes (for example, a maintenance mode) as necessary, and controls on / off of the excitation light source 22 and the calibration light source 24.
The mode can be selected based on a program stored in advance in the converter 40, an instruction from an operation key or the like provided on the converter, or a contact input from a remote instruction center or an instruction by communication. it can.

When the calibration mode is selected, only the calibration light source 24 is turned on by the control of the converter 40. Here, that only the calibration light source 24 is turned on means that other light sources that can affect the detection value of the fluorescence detector 23 are turned off. That is, the excitation light source 22 is turned off. Note that lighting of a light source that does not affect the detection value of the fluorescence detector 23, for example, a display lamp of a display attached to the converter, is not hindered.
In the calibration mode, the calibration light C sequentially passes through the dichroic mirror 26, the wavelength selection filter 34, and the lens 33 constituting the calibration optical system and is guided to the fluorescence detector 23.

In the calibration mode, the converter 40 performs any of the following calibration operations a to e. Which of the following calibration operations is performed may be fixedly selected in advance, a program stored in the converter 40, an instruction from an operation key or the like provided on the converter, or a remote location It may be made arbitrarily selectable based on contact input from the instruction center or an instruction by communication.
a. Based on the detection value of the fluorescence detector 23, it is determined whether an alarm signal needs to be output. When it is determined that an alarm signal needs to be output, an alarm signal is output.
b. Whether or not the calibration data needs to be updated is determined based on the detection value of the fluorescence detector 23. When it is determined that the calibration data needs to be updated, the calibration data is updated.
c. The calibration data is updated based on the detection value of the fluorescence detector 23 without determining whether the calibration data needs to be updated.
d. Both operations a and b are performed.
e. Both operations a and c are performed.

Whether or not an alarm signal needs to be output based on the detection value of the fluorescence detector 23 is determined based on whether or not the detection value of the fluorescence detector 23 is within a predetermined range. Similarly, whether or not the calibration data needs to be updated is determined based on the detection value of the fluorescence detector 23 based on whether or not the detection value of the fluorescence detector 23 is within a predetermined range.
For example, the predetermined range may be a certain range in which the detection value of the fluorescence detector 23 in the previous calibration mode is the median value. Moreover, it can also be set as the fixed range which makes a predetermined fixed value a median. The width of the predetermined range may be appropriately determined according to the normal error range of the fluorescence analyzer 1 and the required accuracy. The predetermined range in determining whether to output an alarm signal may be the same as or different from the predetermined range in determining whether to update calibration data.

  When the detection value of the fluorescence detector 23 is not within the predetermined range, the detection value may be greatly deviated from the detection value that should be originally obtained due to some trouble such as deterioration of the excitation light source 22 or the fluorescence detector 23. There is sex. The administrator of the fluorescence analyzer 1 can confirm whether or not there is a trouble by using an alarm signal. There is no particular limitation on the output format of the alarm signal. The data may be output to a digital or analog display or recorder integrated with or separate from the converter 40, or separated from the converter 40 in the form of a digital or analog output signal. A signal may be transmitted to a body computer or a remote command center. If the detection value of the fluorescence detector 23 is within a predetermined range, the reliability of the calibration data can be confirmed.

  Further, when the detection value of the fluorescence detector 23 is not within the predetermined range, the reliability of the output according to the measurement target component amount in the measurement mode can be ensured by updating the calibration data. On the other hand, when the detection value of the fluorescence detector 23 is within a predetermined range, the continuity of output corresponding to the measurement target component amount in the measurement mode can be ensured by not updating the calibration data.

When updating the calibration data, the converter 40 recognizes the detection value of the fluorescence detector 23 in the calibration mode as a detection value corresponding to the predetermined measurement target component amount, and is stored in advance based on this recognition. Update calibration data.
For example, when the calibration data specifies a calibration curve passing through the origin in the graph where the detection value of the fluorescence detector 23 is the x axis and the measurement target component amount is y, the following updated calibration points are updated. Store as calibration data. Thus, a straight line passing through the updated calibration point and the origin can be specified as an updated calibration curve.
Updated calibration points:
x is a detection value of the fluorescence detector 23 in the calibration mode, and y is the predetermined measurement target component amount.

When the measurement mode is selected, in the fluorescence analyzer 1 of the present embodiment, only the excitation light source 22 is turned on by the control of the converter 40. Here, that only the excitation light source 22 is turned on means that other light sources that can affect the detection value of the fluorescence detector 23 are turned off. That is, the calibration light source 24 is turned off. Note that lighting of a light source that does not affect the detection value of the fluorescence detector 23, for example, a display lamp of a display attached to the converter 40, is not hindered.
In the measurement mode, the excitation light E passes through the lens 31 and the wavelength selection filter 32 constituting the excitation light irradiation optical system, and then is reflected by the dichroic mirror 26 to change the course by 90 degrees, and passes through the cell window 25. It is guided to the overflow surface 17 of the sample water S.
Then, fluorescence F is emitted from the sample water S by the measurement target component in the sample water S, a reaction product with the measurement target component, a reagent that reacts with the measurement target component, and the like.
The fluorescence F sequentially passes through the cell window 25, the dichroic mirror 26, the wavelength selection filter 34, and the lens 33 constituting the fluorescence detection optical system, and is guided to the fluorescence detector 23.

The converter 40 outputs in accordance with the amount of the measurement target component in the sample based on the detection value of the fluorescence detector 23 in the measurement mode and the calibration data stored at that time.
For example, when the calibration data specifies a calibration curve (y = ax) passing through the origin in a graph in which the detection value of the fluorescence detector 23 is the x axis and the measurement target component amount is y, x is in the measurement mode. The y on the calibration curve, which is the detection value of the fluorescence detector 23, is used as the measurement target component amount, and an output corresponding to the measurement target component amount is output.

The content of the information to be output is not particularly limited as long as it corresponds to the amount of the component to be measured. In addition to the amount of component to be measured itself, the amount of reaction product with the component to be measured or the amount of reagent that reacts with the component to be measured. It may be an index that has a correlation with the amount of component to be measured. Alternatively, the output may be performed only when the measurement target component amount is equal to or less than a certain threshold (or less than a certain threshold) or equal to or more than a certain threshold (or exceeds a certain threshold).
Also, the output format is not particularly limited. The data may be output to a digital or analog display or recorder integrated with or separate from the converter 40, or separated from the converter 40 in the form of a digital or analog output signal. A signal may be transmitted to a body computer or a remote command center.

The fluorescence analyzer 1 of this embodiment can measure, for example, the linear alkylbenzene sulfonate concentrations, BOD (biochemical oxygen demand), oil-in-water concentration, phenol concentration, and chlorophyll concentration of sample water. When the concentration of the linear alkylbenzene sulfonate is determined, the wavelength of the excitation light E is 230 nm, and the wavelength of the fluorescence F is 290 nm. When measuring the BOD, the wavelength of the excitation light E is 320 nm, and the wavelength of the fluorescence F is 440 nm. When measuring the oil-in-water concentration, the wavelength of the excitation light E is 230 nm or 365 nm, the wavelength of the fluorescence F is 290 to 360 nm when the wavelength of the excitation light E is 230 nm, and 440 to 460 nm when the wavelength of the excitation light E is 365 nm. . When the phenol concentration is measured, the wavelength of the excitation light E is 250 nm, and the wavelength of the fluorescence F is 300 nm. When measuring the chlorophyll concentration, the wavelength of the excitation light E is 250 to 320 nm, and the wavelength of the fluorescence F is 360 to 370 nm.
In any case, the peak wavelength of the calibration light C is preferably the same as or near the wavelength of the fluorescence F, and particularly preferably the same as the wavelength of the fluorescence F.

  The fluorescence analyzer 1 according to the present embodiment has a simple configuration in which only the calibration light source 24 is added, and can be easily calibrated (update of calibration data, confirmation of the reliability of calibration data) without using a reagent or the like. . In addition, since the optical path by the calibration light detection optical system overlaps most of the optical path by the fluorescence detection optical system, the influence of the fluorescence detection optical system on the detection value of the fluorescence detector 23 by updating the calibration data in the calibration mode. Can be almost adjusted. In addition, since switching between the measurement mode and the calibration mode can be performed only by controlling on / off of the light source, no additional drive mechanism for calibration is required. In addition, since the on / off of the light source can be easily controlled by a program or a command from a remote command center, the calibration operation can be completely automated, and a person can operate for a long time without going to the site.

Second Embodiment
A fluorescence analyzer according to the second embodiment of the present invention will be described. 2, the same components as those in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted. As shown in FIG. 2, the fluorescence analyzer 1 according to this embodiment includes a sample unit 10, a detection unit 50, and a converter 40.
The detection unit 50 includes a light-shielding detection unit case 51 installed on the sample case 11, an excitation light source 22, a fluorescence detector 23, a calibration correction light source 54, and response light detection housed in the detection unit case 51. A container 55 is provided.
The calibration correction light source 54 is disposed at the lower end of the detection unit case 21 so that the light emitting unit 54 a is obliquely above the overflow surface 17. The response light detector 55 is disposed near the lower end of the detection unit case 21 so as to be obliquely above the overflow surface 17.

  A cell window 25 is provided on the lower surface wall of the detection unit case 51 and facing the overflow surface 17. In addition, a cell window 52 is provided at a portion of the lower surface wall of the detection unit case 51 that intersects a line connecting the light emitting unit 54 a of the calibration correction light source 54 and the overflow surface 17. In addition, a cell window 53 is provided at a portion of the lower surface wall of the detection unit case 51 that intersects the line connecting the response light detector 55 and the overflow surface 17. The cell window 52 has a lens shape that converges the calibration light R emitted from the calibration correction light source 54 side to the sample unit 10 on the overflow surface 17. The cell window 53 has a lens shape that causes the response light detector 55 to converge the response light D incident on the detection unit 50 from the sample unit 10 side.

The calibration correction light source 54 is a light source that serves as both the calibration light source and the correction light source of the present invention, and uses a light source that switches between two colors of the calibration light C and the correction light R. The calibration light C is light that can be detected by a fluorescence detector, and the calibration correction light source 54 can emit the calibration light C with a predetermined light amount. Further, the correction light R is light for obtaining response light corresponding to the interference component, that is, light having such a wavelength as to obtain response light corresponding to the interference component in order to correct the influence of the interference component. The calibration correction light source 54 can emit the correction light R with a predetermined light amount. The predetermined amount of light means that the amount of light is known. The predetermined light amount may be a fixed amount or a variable amount that can be appropriately selected by the converter 40.
As the calibration correction light source 54, two chips emitting light of different wavelengths are accommodated in the light emitting part 54a (in a single package) because the light quantity is stable, inexpensive, and small. It is preferable to use a two-chip light emitting diode as described above.
As the response light detector 55, the same one as the fluorescence detector 23 can be used.

In the present embodiment, the excitation light irradiation optical system that guides the excitation light E from the excitation light source 22 to the overflow surface 17 of the sample water S is configured by the lens 31, the wavelength selection filter 32, the dichroic mirror 26, and the cell window 25. .
The fluorescence detection optical system that guides the fluorescence F emitted from the sample water S to the fluorescence detector 23 from the sample water S is constituted by the cell window 25, the dichroic mirror 26, the wavelength selection filter 34, and the lens 33.

The calibration optical system that guides the calibration light C from the calibration correction light source 54 to the fluorescence detector 23 includes a calibration light irradiation optical system and a calibration light detection optical system.
The calibration light irradiation optical system guides the calibration light C from the calibration correction light source 54 to the overflow surface 17 of the sample water S, and is constituted by the cell window 52 in this embodiment.
The calibration light detection optical system guides the calibration light C scattered by the sample water S on the overflow surface 17 from the overflow surface 17 to the fluorescence detector 23. In the present embodiment, the cell window 25, the dichroic mirror 26, the wavelength selection filter 34, and the lens 33 are included. That is, the fluorescence detection optical system of this embodiment also serves as a calibration light detection optical system, and the optical path by the calibration light detection optical system overlaps the entire optical path by the fluorescence detection optical system.

Further, the correction light irradiation optical system that guides the correction light R to the overflow surface 17 of the sample water S is constituted by a cell window 52. That is, the calibration light irradiation optical system of the present embodiment also serves as the correction light irradiation optical system, and the optical path by the calibration light irradiation optical system is the same as the optical path by the correction light irradiation optical system.
The correction light detection optical system that guides the response light D emitted from the sample water S on the overflow surface 17 to the response light detector 55 from the overflow surface 17 is constituted by the cell window 53.

The converter 40 stores calibration data that correlates the detection value of the fluorescence detector 23 and the amount of the measurement target component in the sample water S, similarly to the converter 40 of the first embodiment. Further, the measurement mode, the calibration mode, the correction mode, and other modes (for example, the maintenance mode) are selected as necessary, and the excitation light source 22 and the calibration correction light source 54 (the chip for the calibration light C and the chip for the correction light R) are selected. It controls to turn on and off.
The mode can be selected based on a program stored in advance in the converter 40, an instruction from an operation key or the like provided in the converter, or an instruction from a remote instruction center.

When the calibration mode is selected, only the chip of the calibration light C of the calibration correction light source 54 is turned on by the control of the converter 40. Here, the fact that only the chip of the calibration light C of the calibration correction light source 54 is turned on means that other light sources that may affect the detection value of the fluorescence detector 23 are turned off. In other words, the correction light R chips of the excitation light source 22 and the calibration correction light source 54 are turned off. Note that lighting of a light source that does not affect the detection value of the fluorescence detector 23, for example, a display lamp of a display attached to the converter 40, is not hindered.
In the calibration mode, the calibration light C passes through the cell window 52 constituting the calibration light irradiation optical system of the calibration optical system and reaches the overflow surface 17. Then, after being scattered by the overflow surface 17, the light passes through the cell window 25, the dichroic mirror 26, the wavelength selection filter 34, and the lens 33, which constitute the calibration light detection optical system of the calibration optical system, to the fluorescence detector 23. Led.

In the calibration mode, the converter 40 performs any of the following calibration operations a to e. Which of the following calibration operations is performed may be fixedly selected in advance, a program stored in the converter 40, an instruction from an operation key or the like provided on the converter, or a remote location It may be made arbitrarily selectable based on contact input from the instruction center or an instruction by communication.
a. Based on the detection value of the fluorescence detector 23, it is determined whether an alarm signal needs to be output. When it is determined that an alarm signal needs to be output, an alarm signal is output.
b. Whether or not the calibration data needs to be updated is determined based on the detection value of the fluorescence detector 23. When it is determined that the calibration data needs to be updated, the calibration data is updated.
c. The calibration data is updated based on the detection value of the fluorescence detector 23 without determining whether the calibration data needs to be updated.
d. Both operations a and b are performed.
e. Both operations a and c are performed.
The specific contents of each calibration operation are the same as those of the fluorescence analyzer 1.

When the correction mode is selected, only the chip of the correction light R of the calibration correction light source 54 is turned on by the control of the converter 40. Here, the fact that only the chip of the correction light R of the calibration correction light source 54 is turned on means that other light sources that can affect the detection value of the response light detector 55 are turned off. That is, the calibration light C chips of the excitation light source 22 and the calibration correction light source 54 are turned off. Note that lighting of a light source that does not affect the detection value of the response light detector 55, for example, a display lamp of a display attached to the converter 40, is not hindered.
In the correction mode, the correction light R passes through the cell window 52 constituting the correction light irradiation optical system of the correction optical system and reaches the overflow surface 17. The response light D obtained as a result passes through the cell window 53 constituting the correction light detection optical system and is guided to the response light detector 55. This response light D corresponds to the disturbing component of the sample water S.

The converter 40 of the present embodiment uses, as a correction function, the relationship between the calibration data and the detection value of the response light detector 55 corresponding to the disturbing component of the sample water S and the amount of influence on the detection value of the fluorescence detector 23. I remember it. It is preferable that the correction function is created by initial calibration using a standard sample in which a predetermined reagent, a measurement target component amount, and an interference component are known after the manufacture of the fluorescence analyzer 1.
When the correction mode is selected, the converter 40 obtains a correction amount for correcting the measurement target component amount in the sample based on the calibration data, based on the detection value of the response light detector 55 and the correction function.
For example, when the calibration data specifies a calibration curve (y = ax) passing through the origin in a graph in which the detection value of the fluorescence detector 23 is the x axis and the measurement target component amount is y, the correction amount b is Seek and remember. As a result, the corrected calibration curve (y = ax + b) can be specified, and the measurement target component amount in the sample corrected from the calibration curve can be obtained.

When the measurement mode is selected, in the fluorescence analyzer 2 of this embodiment, only the excitation light source 22 is turned on under the control of the converter 40. Here, that only the excitation light source 22 is turned on means that other light sources that can affect the detection value of the fluorescence detector 23 are turned off. That is, all the calibration correction light sources 54 are turned off. Note that lighting of a light source that does not affect the detection value of the fluorescence detector 23, for example, a display lamp of a display attached to the converter 40, is not hindered.
In the measurement mode, the excitation light E is guided to the overflow surface 17 of the sample water S by the excitation light irradiation optical system, and the fluorescence F emitted from the sample water S is guided to the fluorescence detector 23 by the fluorescence detection optical system.

The converter 40 outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector 23 in the measurement mode, the calibration data stored at that time, and the correction amount. The contents and format of the information to be output are the same as in the first embodiment.
For example, when the calibration curve specified by the correction is y = ax + b in a graph in which the detection value of the fluorescence detector 23 is the x axis and the measurement target component amount is y, x is the detection of the fluorescence detector 23 in the measurement mode. The value y on the calibration curve is set as a measurement target component amount, and an output corresponding to the measurement target component amount is output.
If the correction amount is not stored, an output corresponding to the amount of the measurement target component in the sample is output based only on the calibration data.

The fluorescence analyzer 2 of the present embodiment can measure, for example, the concentration of linear alkylbenzene sulfonates, BOD (biochemical oxygen demand), oil-in-water concentration, phenol concentration, and chlorophyll concentration of sample water.
The most common disturbing component of a fluorescence analyzer is the turbid component. In general, when a turbid component is contained in the sample water S, the fluorescence F emitted from the sample water S is absorbed. Therefore, in any of the fluorescence analyzers, the response light D corresponding to the turbid component that is the interfering component is used, and the output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector 23 and the calibration data. Is preferably corrected.
In order to obtain the response light D corresponding to the turbid component, it is preferable to use light having a peak wavelength of 660 nm or a wavelength near the correction light R as the response light D. In this case, the angle formed by the optical axis of the correction light R and the optical axis of the response light D is preferably 100 ° to 130 °.

The fluorescence analyzer 1 of the present embodiment has a simple configuration in which a calibration correction light source 54 and a response light detector 55 are simply added, and can be easily calibrated without using a reagent or the like (update of calibration data, reliability of calibration data). In addition, the influence of interfering components on the fluorescence measurement can be corrected. Further, since the optical path by the calibration light detection optical system overlaps the entire optical path by the fluorescence detection optical system, the influence of the entire fluorescence detection optical system on the detection value of the fluorescence detector 23 by updating the calibration data in the calibration mode. Can be adjusted. Among the fluorescence detection optical systems, the cell window 25 is particularly prone to problems such as contamination, and the inclusion of the cell window 25 in the optical path of the calibration light detection optical system increases the reliability of calibration. .
Further, since the measurement mode, the calibration mode, and the correction mode can be switched only by the on / off control of the light source, no additional drive mechanism for calibration or correction is required. In addition, since the on / off of the light source can be easily controlled by a program or a command from a remote command center, the calibration operation can be completely automated, and a person can operate for a long time without going to the site.

<Other embodiments>
The fluorescence analyzer of the present invention may be one in which the response light detector 55 and the cell window 53 in the fluorescence analyzer 2 of the second embodiment are omitted. In that case, although the interference component cannot be corrected by the fluorescence analyzer 2 itself, the optical path by the calibration light detection optical system overlaps the entire optical path by the fluorescence detection optical system, so that the fluorescence analysis apparatus 1 of the first embodiment is more than that. There is an advantage that the reliability of the calibration is increased.
In the present embodiment, the excitation light F, the calibration light C, and the correction light R are each described as single light, but may be a combination of two or more colors. For example, if the wavelength selection filter 32 that selects the wavelength of the excitation light source 22 can be selected by switching two wavelengths, the excitation light E of two colors corresponding to different measurement target components can be switched and emitted. Further, when measuring a plurality of components to be measured, if the wavelengths of the respective fluorescence F are different, the calibration light C of the calibration light source 24 and the calibration correction light source 54 may be selected from a plurality of wavelengths. At this time, light emitting diodes of two chips or three chips or more can be appropriately used for the calibration light source 24 and the calibration correction light source 54.
The converter 40 may be capable of storing a history of calibration and correction.

  The fluorescence analyzer of the present invention can be used as a water quality analyzer for determining linear alkylbenzene sulfonate concentrations, BOD (biochemical oxygen demand), oil-in-water concentration, phenol concentration, and chlorophyll concentration of sample water. In addition, the fluorescence (including intensity and quenching time) of the measurement target component, the reaction product of the measurement target component, or the reagent that reacts with the measurement target component is measured by the fluorescence emitted from the sample, and the presence / absence of the measurement target component and / or Alternatively, the present invention can be widely applied to any fluorescence analyzer that measures the concentration or the fluorescence characteristics (fluorescence spectrum, excitation spectrum, etc.) itself.

For example, there is a uranium quantification method for detecting or quantifying a phosphor containing a test substance. There is a method of analyzing aluminum by converting a sample which is a non-fluorescent substance into a fluorescent substance by a chemical reaction and utilizing the fluorescence for analysis. In addition, there is a method for measuring thallium by measuring the fluorescence quenching of rhodamine B and the like using a fluorescent substance as a reagent and utilizing the disappearance of fluorescence due to reaction with a sample.
In addition, neutralization, redox, precipitation and complexometric titration using fluorescence generation, disappearance, or discoloration of a fluorescent indicator to indicate the end point of titration, or by measuring luminescence by oxidation of formaldehyde in a basic solution. It may be used to measure formaldehyde.
In addition, chemiluminescence measurement such as dry atmospheric SO ₂ concentration measurement (dry AP meter) by measuring the emission intensity of the thermal decomposition product of sulfur dioxide (SO ₂ ) is also given as an example. In addition, a fluorescent immunoassay method (fluorescence immunoassay) is also used in which an antigen or antibody is labeled with a fluorescent substance, the antigen-antibody reaction is quantitatively tracked using the decrease in fluorescence intensity due to the antigen-antibody reaction, and the antigen or antibody is measured. Can be used.

DESCRIPTION OF SYMBOLS 1, 2 ... Fluorescence analyzer 10 ... Sample part 20, 50 ... Detection part, 40 ... Converter
DESCRIPTION OF SYMBOLS 11 ... Sample case, 12 ... Sample tank, 13 ... Cylindrical body, 17 ... Overflow surface,
21, 51, detection unit case, 22, excitation light source, 23, fluorescence detector, 24, calibration light source,
25 ... Cell window, 26 ... Dichroic mirror, 54 ... Calibration correction light source,
55. Response light detector,
S ... sample water, E ... excitation light, F ... fluorescence, C ... calibration light, R ... correction light, D ... response light

Claims (3)

An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence from the sample A fluorescence detection optical system that leads to the fluorescence detector; a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector; a calibration optical system that guides the calibration light from the calibration light source to the fluorescence detector; A calibration that stores calibration data that correlates the detection value of the fluorescence detector and the amount of the measurement target component in the sample, and that performs output according to the amount of the measurement target component in the sample based on the detection value of the fluorescence detector Equipped with
The calibration optical system includes a calibration light irradiation optical system that guides the calibration light from the calibration light source to the sample, and a calibration light detection optical system that guides the calibration light scattered by the sample from the sample to the fluorescence detector. The fluorescence detection optical system also serves as the calibration light detection optical system,
The converter outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector and the calibration data when only the excitation light source is turned on, and turns on only the calibration light source. A fluorescence analyzer characterized by determining whether or not an alarm signal needs to be output based on a detection value of the fluorescence detector at the time, and outputting an alarm signal when it is determined that an alarm signal needs to be output. An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the liquid sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence A fluorescence detection optical system that guides the sample from the sample to the fluorescence detector, a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector, and calibration optics that guides the calibration light from the calibration light source to the fluorescence detector A correction light source that emits a predetermined amount of correction light, and a response light detector that detects the response light emitted from the sample by the correction light, in order to obtain response light according to the interference component of the system, A correction light irradiation optical system for guiding the correction light to the sample, a response light detection optical system for guiding the response light from the sample to the response light detector, a detection value of the fluorescence detector, and a measurement object in the sample The amount of ingredients Stores the calibration data characterizing communication, comprising a converter for an output corresponding to the measurement target component of the sample based on a detection value of the fluorescence detector,
The optical path by the calibration optical system overlaps at least a part of the optical path by the fluorescence detection optical system,
The converter outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector and the calibration data when only the excitation light source is turned on, and turns on only the calibration light source. When it is determined that the output of the alarm signal is necessary based on the detection value of the fluorescence detector at the time, and when it is determined that the output of the alarm signal is necessary, the alarm signal is output and only the correction light source is turned on. Based on the detection value of the response light detector at the time when the excitation light source is turned on, the detection value of the fluorescence detector when only the excitation light source is turned on and the output corresponding to the measurement target component amount in the sample based on the calibration data are corrected A fluorescence analyzer characterized by: An excitation light source that emits excitation light, a fluorescence detector that detects fluorescence emitted from the liquid sample by the excitation light, an excitation light irradiation optical system that guides the excitation light from the excitation light source to the sample, and the fluorescence A fluorescence detection optical system that guides the sample from the sample to the fluorescence detector, a calibration light source that emits a predetermined amount of calibration light that can be detected by the fluorescence detector, and calibration optics that guides the calibration light from the calibration light source to the fluorescence detector A correction light source that emits a predetermined amount of correction light, and a response light detector that detects the response light emitted from the sample by the correction light, in order to obtain response light according to the interference component of the system, A correction light irradiation optical system for guiding the correction light to the sample, a response light detection optical system for guiding the response light from the sample to the response light detector, a detection value of the fluorescence detector, and a measurement object in the sample The amount of ingredients Stores the calibration data characterizing communication, comprising a converter for an output corresponding to the measurement target component of the sample based on a detection value of the fluorescence detector,
The light emitting unit of the calibration light source and the light emitting unit of the correction light source are housed in a single package,
The calibration optical system includes a calibration light irradiation optical system that guides the calibration light from the calibration light source to the sample, and a calibration light detection optical system that guides the calibration light scattered by the sample from the sample to the fluorescence detector. Become
The calibration light irradiation optical system also serves as the correction light irradiation optical system,
The fluorescence detection optical system also serves as the calibration light detection optical system,
The converter outputs an output corresponding to the measurement target component amount in the sample based on the detection value of the fluorescence detector and the calibration data when only the excitation light source is turned on, and turns on only the calibration light source. When it is determined that the output of the alarm signal is necessary based on the detection value of the fluorescence detector at the time, and when it is determined that the output of the alarm signal is necessary, the alarm signal is output and only the correction light source is turned on. Based on the detection value of the response light detector at the time when the excitation light source is turned on, the detection value of the fluorescence detector when only the excitation light source is turned on and the output corresponding to the measurement target component amount in the sample based on the calibration data are corrected A fluorescence analyzer characterized by:

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