JPH10206313A - Feeble light measuring apparatus, sample vessel and feeble light measuring system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To measure the feeble light with high accuracy in a feeble light measuring apparatus, a sample vessel and a feeble light measuring system used to measure the scattered feeble light. SOLUTION: A sample vessel 20 having a sample receiving part 21-1 to receive a measuring object sample and a sample receiving part 21-2 to receive a dummy sample, is arranged in an upper light shielding sample chamber 11 provided in a feeble light measuring apparatus 10, and the measuring light 100 and the background light 101-1 and 101-2 are emitted downward, and a light receiving circuit 30 having two light receiving elements 31-1 and 31-2 and a differential amplifier 32, is arranged in a light shielding light receiving chamber 12 partitioned by a light transmissive window 13, and the light shielding light receiving chamber 12 is put in a vacuum and at a very low temperature at measuring time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weak light measuring instrument, a sample container, and a weak light measuring system used for measuring scattered weak light.

[0002]

2. Description of the Related Art Weak light detection technology is expected to be applied to a wide range of applications such as biology, medicine, astronomy, and food and nutrition. In particular, the detection of weak light in the 1 μm wavelength band from so-called singlet oxygen, which is one of active oxygen and placed in a specific excited state, is important in academic and application aspects, but is difficult with conventional techniques. Yes, it is expected to break this.

[0003] While singlet oxygen plays an important role in host defense, it can also have an adverse effect on living organisms, and it is important to search for substances that produce and remove singlet oxygen. A detection system that can perform this is required.

[0004]

Conventionally, a photomultiplier tube (PMT) or the like has been used for detecting weak light. However, the photomultiplier tube has a small quantum efficiency of several percent or less and is an electron tube. The size is large, and cooling is required to reduce noise, but it is difficult to cool the temperature to minus 80 degrees or less, which is problematic. The container holding the sample to be measured, which is integrated with such an apparatus, is a mere container made of a material through which light emitted from the sample can pass, and cannot efficiently guide weak light to the photodetector. .

[0005] Singlet oxygen plays a very important role in living organisms, and its detection has conventionally employed many complicated chemical detection methods. Recently, a system using a photomultiplier tube has been able to detect weak light with a wavelength of 700 to 800 nm. However, since it cannot be completely distinguished from light from other luminescent species, it is necessary to detect luminescence in the 1 μm band. The necessity of was pointed out. However, only studies on singlet oxygen made by mixing chemical substances have been made, and no emission in the 1 μm band from singlet oxygen in biological model systems or in vivo has been measured.

In view of the above circumstances, an object of the present invention is to provide a weak light measuring device, a sample container, and a weak light measuring system suitable for measuring weak light.

[0007]

For example, there is no method other than improving the S / N ratio to the utmost in order to detect weak emission in the 1 μm band from singlet oxygen in a living body model system or a living body. In order to improve the S / N ratio, (a) the light receiving element is cooled to reduce the dark current, (b) light from the sample is efficiently guided to the light receiving element, and (c) light other than light emitted from the sample. And electrical noise must be eliminated.

The sample to be measured is, for example, a living body, and it is difficult to cool it like a light receiving element. Therefore, heat radiation (hereinafter referred to as background light) from the device under test and its containers is a large noise source. If the wavelength of the measurement light emitted from the object to be measured is known, a considerable amount of background light can be removed by an optical filter that passes only that wavelength, but background light in the same wavelength region as the light to be measured cannot be removed.

SUMMARY OF THE INVENTION The present invention is intended to hold a sample and efficiently guide light emitted from the sample to a light receiving element, and to remove background light which could not be removed conventionally. To achieve the above object, the present invention provides: (1_1) a sample receiving portion for receiving a sample, the sample receiving portion having an emission window for emitting light emitted from the received sample; A light-shielding sample chamber (2) in which two sample containers having windows arranged in the same plane and facing in the same direction are detachably arranged such that the emission windows of these two sample receiving portions face downward. 1_2) The light source is formed below the light-shielding sample chamber with a light-transmitting window made of a light-transmitting member that transmits light emitted downward from two emission windows of the sample container placed in the light-shielding sample chamber interposed therebetween. Two light-receiving elements arranged with their light-receiving surfaces facing upward to amplify the difference between these two light-receiving signals by receiving each light emitted from each of the emission windows and passing through each light-transmitting window to obtain each light-receiving signal. Receiving amplifier including Characterized by comprising a light-shielding receiving chamber road is located.

Here, in the weak light measuring device of the present invention, it is preferable that the light transmitting member constituting the light transmitting window is formed by forming an optical filter that selectively transmits light having a desired wavelength. In a preferred embodiment of the weak light meter according to the present invention, an optical filter for selectively transmitting light of a desired wavelength is provided in front of the light receiving surfaces of the two light receiving elements.

Further, in the weak light measuring device according to the present invention, two optical filters are provided independently of each other in correspondence with each of the exit windows, between the exit window and the translucent window. And the translucent window is
It is also preferable to include two light-transmitting windows which are provided independently of each other and correspond to each of the two light-emitting windows. In a preferred embodiment, a chopper for chopping light incident on the two light receiving elements with a predetermined phase relationship with each other is provided in front of the two light receiving elements in the light-shielded light receiving chamber.

A sample container according to the present invention, which fulfills the above object, comprises: (2_1) a first sample receiving section (2_2) having an emission window for receiving a sample therein and emitting light emitted from the received sample. An emission window for receiving the sample and emitting light emitted from the received sample is provided, and the emission window is provided with the first window.
A second sample receiving portion arranged in the same plane as the emission window of the sample receiving portion and oriented in the same direction as the first sample receiving portion.

Here, in the sample container of the present invention,
Each sample received in each of the first and second sample receiving portions was emitted from a portion of the inner wall of the first and second sample receiving portions except for the emission windows of the first and second sample receiving portions. It is preferable that each of the first and second sample receiving sections has a reflecting surface for reflecting the light toward the respective exit window.

In the sample container of the present invention, each light emitted from each sample received in the first and second sample receiving portions is collected in the emission window of each of the first and second sample receiving portions. It is also a preferable embodiment to provide each light condensing member that emits light. Further, in the sample container of the present invention,
For each of the first and second sample receiving sections,
A plurality of solution inlets, respective solution inflow paths into which solutions flowing from the plurality of solution inlets are mixed and flow into the first and second sample receiving portions, respectively, and the first and second sample receiving portions; It is preferable to provide each solution outflow path for each of the solutions received in the first solution to flow out.

Further, in a preferred embodiment, the sample container of the present invention further comprises a detachable lid for opening the side of the first and second sample receiving portions facing the emission window. Furthermore, it is preferable that the sample container of the present invention further includes a means for maintaining the sample container at a predetermined temperature. Further, the weak light measurement system of the present invention, which fulfills the above-mentioned object, comprises: (3_1) a first sample receiving portion provided with an emission window for receiving a sample therein and emitting light emitted from the received sample;
An emission window for receiving the sample therein and emitting light emitted from the received sample, the emission window being arranged on the same plane as the emission window of the first sample receiving portion and oriented in the same direction; A plurality of solution inlets and a plurality of solution inlets respectively flowed in corresponding to the second sample receiving portion arranged side by side in the sample receiving portion, and the first and second sample receiving portions, respectively. A solution inflow path into which the solution is mixed and flows into each of the first and second sample receiving sections; and a solution outflow path through which each solution received in each of the first and second sample receiving sections flows out. A first sample container provided with a solution flow path comprising: (3_2) a third sample receiving portion having an emission window for emitting light emitted by the received sample, the sample receiving portion receiving the sample inside;
An emission window for receiving the sample therein and emitting light emitted from the received sample, wherein the emission window is arranged on the same plane as the emission window of the third sample receiving portion and faces in the same direction as the third window. A second sample container comprising: a fourth sample receiving portion arranged side by side with the sample receiving portion; and a detachable lid that opens a side of the third and fourth sample receiving portions facing the emission wall. (3_3) The light-shielding sample chamber in which the first and second sample containers are interchangeably arranged with the emission window facing downward, and the first and second sample containers arranged in the light-shielding sample chamber. It is formed below the light-shielding sample chamber with a light-transmitting window made of a light-transmitting member that transmits light emitted downward from the two emission windows, and is emitted from each of the two emission surfaces and transmitted through the light-transmitting window. Each light is received individually and each light reception signal is A weak light measuring device having a light-shielded light-receiving chamber in which a light-receiving circuit including two light-receiving elements arranged so that the light-receiving surface faces upward and an amplifier for amplifying a difference between the two light-receiving signals is provided. It is characterized by the following.

Here, in the weak light measurement system of the present invention, light is directed toward each of the two light receiving elements which are interchangeably disposed in the light-shielded sample chamber with the first and second sample containers. It is preferable to provide a calibration jig for receiving the two illuminants emitted. Further, in the weak light measurement system of the present invention, a sample supply tank for storing a sample supplied to the sample container, a waste liquid receiving tank for receiving waste liquid from the sample container, and a sample liquid level in the sample supply tank. It is also preferable to provide a liquid level difference adjusting means for freely adjusting the difference between the height of the waste liquid and the height of the waste liquid level in the waste liquid receiving tank.

Further, in the weak light measurement system according to the present invention, two check valves permitting the flow of the sample in the same direction at positions close to each other in the conduit for introducing the sample into the sample container. It is also a preferable embodiment to provide a sample quantitative supply device having a piston for allowing a sample to flow into and branch out of a pipe from a pipe connecting two check valves.

[0018]

Embodiments of the present invention will be described below. 1 to 3 are schematic cross-sectional views and a side view, respectively, showing an embodiment of the weak light measuring device of the present invention in a state where an embodiment of the sample container of the present invention is disposed inside. FIG. 2 is a schematic cross-sectional view as viewed from above, and a schematic cross-sectional view as viewed from above.

The weak light measuring device 10 shown here has a light-shielding sample chamber 11 in which a sample container 20 is removably arranged, and a light-shielding light-receiving chamber 12 in which a light-receiving circuit 30 is arranged. The light-shielded sample chamber is kept at atmospheric pressure and room temperature, and the light-shielded light-receiving chamber 12 is kept at vacuum and cryogenic temperature for measurement. The light-shielding sample chamber 11 is formed above the light-shielding light-receiving chamber 12, and between the light-shielding sample chamber 11 and the light-shielding light-receiving chamber 12, an optical element selectively transmitting 1.268 μm light from singlet oxygen. It is partitioned by a light-transmitting window 13 also serving as a filter. Further, the light-shielding sample chamber 11 is provided with a door 14 for taking the sample container 20 in and out.

The sample container 20 has two sample receiving chambers 21_1 and 21_2 for receiving the respective samples, and the lower surfaces of the sample receiving chambers 21_1 and 21_2 have the lower surfaces of the respective samples received in the respective sample receiving chambers 21_1 and 21_2. Outgoing windows 22_1 and 22_2 for emitting the light emitted from are formed, and converging quartz lenses 23_1 and 23_2 are arranged in the respective outgoing windows 22_1 and 22_2. Also,
Exit window 2 on the inner wall surface of each sample receiving chamber 21_1, 21_2
The portions 21_1a and 21_2a except for 2_1 and 22_2 are plated with gold, and are configured to reflect light emitted from each sample received therein toward each of the emission windows 22_1 and 22_2. In addition, the sample container 20 corresponds to each of the sample receiving chambers 21_1 and 21_2,
Three solution inlets 24_1a and 24_1 respectively for injecting a solution into each of the sample receiving chambers 21_1 and 21_2.
b, 24_1c; 24_2a, 24_2b, 24_2c
And one solution outlet 25_1 and 25_2, respectively.

Further, the sample container 20 has an inlet 26, an internal channel 27, and an outlet 28 for the constant temperature circulating water W for maintaining the sample container 20 at a constant temperature. The sample container 20 shown in FIGS. 1 to 3 is a so-called rapid mixing container that instantaneously mixes a plurality of solutions to form a sample, and is suitable for measuring an in vitro (enzymatic) sample. .

Three solution inlets 24_1 provided corresponding to the two sample receiving portions 21_1 and 21_2, respectively.
a, 24_1b, 24_1c; 24_2a, 24_2
b, 24_2c, each syringe (injector) 41_1a, 41_1b, 41_1 constituting the ultra-high-speed dispenser 40
c; 41_2a, 41_2b, 41_2c are connected and their syringes 41_1a, 41_1b, 41
_1c; 41_2a, 41_2b, 41_2c to each solution inlet 24_1a, 24_1b, 24_1c;
When each solution is injected via 2a, 24_2b, 24_2c, the solutions are injected into the three solution inlets 24_1a, 24_1b, 24_1c; 24_2a, 2
4_2b, 24_2c and each sample receiving section 21_1, 21_
Each sample is instantaneously mixed in the middle of each of the solution inflow paths 29_1 and 29_2 connecting the sample Nos. 2 and 2, and is injected into each sample receiving portion 21_1 and 21_2 in a time of several tens ms or less in this embodiment. Each sample receiving part 21_1, 21_2 has a volume of 200 to 500 microliters. The samples overflowing from the sample receiving portions 21_1 and 21_2 are discharged to the outside of the sample container 20 via the solution outlets 25_1 and 25_2.

Each syringe 41_1a, 41_1b, 41
_1c; 41_2a, 41_2b, and 41_2c contain the respective solutions S, B, A; So, C, A as shown in FIG. Here, A + B is 1.26 from singlet oxygen.
A weak light of 8 μm is emitted, and the emission intensity is measured by adding S. For example, if light emission is extinguished by the addition of S, S is a solution having a strong singlet oxygen scavenging ability. A + C does not emit light, but the mixing condition is A + B
Use something close to. By doing so, the background light (background) can be subtracted as described later. So is the same solution as the solvent of S, and the background light can be accurately subtracted by injecting So at the same time as S is injected. For example, A is a hypochloride solution (NaOCl), B is a hydrogen peroxide solution (H ₂ O ₂ ), C is water (H ₂ O), and S is a singlet oxygen erasing substance solution (S Various substances are tried,
For example, a carotene solution) and So are solutions in which a singlet oxygen eliminating substance is dissolved (when S is carotene, a solution in which carotene is dissolved).

As described above, the two sample receiving portions 21
_1 and 21_2 in one sample receiving section 21_1,
When the sample to be measured is injected, one of the sample receiving portions 21
_1, the measurement light 100 (in this example, light with a wavelength of 1.268 μm due to singlet oxygen) and the background light 101_1
Is emitted through the emission window 22_1 and the quartz lens 23_1. On the other hand, the two sample receiving portions 21_1 and 21_
2, a dummy sample is injected into the other sample receiving portion 21_2, and the background light 10 from the sample receiving portion 21_1 is injected.
Background light 101_2 having the same wavelength distribution and the same intensity as 1_1
Is emitted through the emission window 22_2 and the quartz lens 23_2. In the example shown here, the emission window 22_
Although both the lenses 22_1 and 22_2 and the quartz lenses 23_1 and 23_2 are provided, the quartz lenses 23_1 and 23_2 may be omitted and only the flat emission windows 22_1 and 22_2 may be provided, or the flat emission windows 22_1 and 22_2 may be provided. Omit
Only the quartz lenses 23_1 and 23_2 may be provided.

The light-shielding light-receiving chamber 12 has a sample light-receiving section 21_1.
A light-receiving element 31_1 having a light-receiving surface facing upward is provided at a position facing the light-emitting window 22_1 with the light-transmitting window 13 interposed therebetween. In addition, the light-transmitting window 13_2 is provided with respect to the light-emitting window 22_2 of the sample light-receiving section 21_2. Another light receiving element 31_2 having a light receiving surface facing upward is provided at a position facing each other with the light receiving element 31_2 therebetween. The two light receiving signals obtained by the two light receiving elements 31_1 and 31_2 are input to a differential amplifier 32 as a preamplifier, and the difference between the two light receiving signals is calculated and the difference is amplified.

As described above, the measurement light 100 and the background light 101_1 are emitted from the sample receiving portion 21_1 into which the sample to be measured is injected out of the two sample receiving portions 21_1 and 21_2. 13 as it is and enters the light receiving element 31_1, and the background light 101_1 is weakened by the filter function of the light transmitting window 13 and is thus received by the light receiving element 31_1.
And the light receiving element 31_1 receives the measurement light 10
0 and the background light 101_1 weakened by the light transmitting window 13 are received.

On the other hand, the two sample receiving portions 21_1 and 21_
Sample receiving portion 21_2 into which the dummy sample of the sample No. 2 has been injected
, The background light 101_2 is emitted, is weakened by the filter function of the light transmitting window 13, and enters the light receiving element 31_2, and the light receiving element 31_2 receives the weakened background light 10_2.
1_2 is received. This background light 101_2 has the same intensity as the background light 101_1. Therefore, in the differential amplifier 32, the background light 101_1 and the background light 101_2 are canceled each other, and a signal proportional to the intensity of the measurement light 100 is output from the differential amplifier 32. A specific configuration of the light receiving circuit 30 is disclosed in Japanese Patent Application No. Hei 8-032235.
The circuit proposed in the above is preferred.

It should be noted that here, the 2
Quartz lens 2 for condensing light into two emission windows 22_1 and 22_2
3_1 and 23_2, and the light-transmitting window 13 has been described as having a filtering function. However, the light-transmitting window 13 may have a function of a condenser lens, and the light-emitting windows 22_1 and 22_2 may have the function of an optical filter. Alternatively, the optical filter 15_ may be provided on the front surface of the light receiving elements 31_1 and 31_2.
1, 15_2 may be provided.

Next, another embodiment of the weak light measuring device of the present invention will be described. FIG. 4 is a sectional view showing a second embodiment of the weak light measuring instrument according to the present invention. The weak light measuring device 110 shown here is similar to the weak light measuring device 10 shown in FIG.
Emission windows 122_1 and 122_ for emitting light emitted from a sample
A sample container 120 having sample receiving portions 121_1 and 121_2 each having a sample holder 120 is provided with a light-shielding sample chamber 111 in which the sample container 120 is detachably mounted, and is formed below the light-shielding sample chamber 111 and is arranged with the light receiving surface facing upward. Two light receiving elements 131_1 and 131_2 and these two light receiving elements 13
The light receiving circuit 112 includes a light receiving circuit 130 including a differential amplifier 132 for amplifying a difference between light receiving signals from the light receiving signals 1_1 and 131_2. 115 is an emission window 122
_1, 122_2 and the light transmitting window 113. The position where the optical filter is arranged may be any position between the light transmitting window and the light receiving element or between the light emitting window and the light transmitting window. May also be used.

Next, a third embodiment of the weak light meter according to the present invention will be described. FIG. 5 is a sectional view showing a weak light measuring device according to a third embodiment of the present invention. The weak light measuring device 210 shown here has a configuration similar to that of the weak light measuring device 110 shown in FIG.
The light-shielding sample chamber 211 and the light-shielding light-receiving chamber 212 similar to the light-shielding sample chamber 111 in FIG. The weak light measuring device 210 shown in FIG. 5 is different from the weak light measuring device 110 shown in FIG.
_1 and 222_2, and two optical filters 215_1 and 215_2 provided independently of each other in correspondence with each of the emission windows, respectively, between the light transmission windows.
Two translucent windows 213_1, 213_2 provided independently of each other corresponding to the two emission windows 222_1, 222_2.
It consists of

As described above, in the third embodiment,
Optical filters 215_1, 215_2 and translucent window 21
3_1 and 213_2 are two sample receiving sections 221_1 and 221_1.
21_2. Therefore, it is possible to prevent the lights emitted from the emission windows 222_1 and 222_2 of the two sample receiving portions 221_1 and 221_2 from interfering with each other, and to minimize crosstalk.

Next, a fourth embodiment of the weak light measuring device of the present invention will be described. FIG. 6 is a sectional view showing a fourth embodiment of the weak light measuring instrument according to the present invention. The weak light measuring device 310 shown here has a configuration similar to that of the weak light measuring device 210 shown in FIG.
, A light-shielding sample chamber 311 and a light-shielding light-receiving chamber 312 similar to the light-shielding sample chamber 211 and the light-shielding light-receiving chamber 212 are provided. The weak light measuring device 310 shown in FIG. 6 is different from the weak light measuring device 210 shown in FIG.
2, a rotary shutter type chopper 71 for chopping light incident on the two light receiving elements 331_1 and 331_2 with a predetermined phase relationship on the front surface of the two light receiving elements 331_1 and 331_2 and a chopper drive for driving the same. This is the point that the unit 72 is provided.

As described above, the light receiving elements 331_1 and 331
By chopping the light incident on _2, the signal light is converted into a frequency at which the 1 / f noise is sufficiently reduced, and the effect of the 1 / f noise generated from the light receiving element or the electronic circuit on the light receiving signal is suppressed. it can. As the chopper, a chopper using a tuning fork or an electromagnetic or electronic chopper may be used instead of the rotary shutter chopper. The signal converted to electricity by the light receiving element is
Although it can be converted into an AC signal by an electronic circuit, this method cannot remove noise generated from the light receiving element itself, so that mechanical chopping is preferable. Note that the chopper 71 may modulate the two received light signals in phase.
Alternatively, modulation may be performed in the opposite phase.

Next, the sample container of the present invention used in the weak light measuring device of each of the above embodiments will be described. FIG.
FIG. 4 is a view showing another type of sample container which is disposed in the light-shielded sample chamber 11 so as to be interchangeable with the sample container 20 shown in FIGS. The sample container 50 has two cylindrical sample receiving portions 51.
_1 and 51_2 are formed, and the sample receiving portions 51_ are provided on the lower surfaces of the two sample receiving portions 51_1 and 51_2.
1, 51_2 are formed with emission windows 52_1, 52_2 for emitting light emitted from the sample received therein, and the emission windows 52_1, 52_2 are further provided with respective quartz lenses 53 for focusing.
_1 and 53_2 are fixed. However, in the example shown in FIG. 7, although both the exit windows 52_1 and 52_2 and the quartz lenses 53_1 and 53_2 are provided, the quartz lenses 53_1 and 53_2 are omitted, and
2_1 and 52_2 may be provided, and the flat emission windows 52_1 and 52_2 are omitted, and the quartz lens 53_1 and 52_2 are omitted.
Only 53_2 may be provided.

The sample container 50 has a sample receiving section 5.
A fixed temperature circulating water inlet 56 and a member 50B formed with an unillustrated outlet are fixed to the upper part of the member 50A in which the 1_1 and 51_2 are formed, and the constant temperature circulating water flows in from the inlet 56, The sample flows out of the outlet through the internal flow path 57, whereby the sample container 50 is maintained at a constant temperature.

The sample container 50 has a detachable lid 5 for closing the upper surfaces of the two sample receiving portions 51_1 and 51_2.
9 are provided. Two sample receiving portions 51_1 and 51
_2 cylindrical side surface 51_1a, 51_2, and lid 5
9 is provided with gold plating for reflecting the light emitted from the sample on portions forming the upper surfaces of the two sample receiving portions 51_1 and 51_2.

The sample container 50 shown in FIG. 7 is a so-called cuvette type container, which is suitable for measuring in vivo systems (cells and tissues). In this case, the cells and the like are attracted by gravity and settle at the bottom, so that the cells and the like
_1 and 31_2 (see FIGS. 1 to 3) are arranged with the emission surfaces 52_1 and 52_2 of the sample container 50 facing downward as close as possible.

In the case of the rapid mixing type sample container 20 shown in FIGS. 1 to 3, the solution is injected by a syringe. In the case of the cuvette type sample container 50 shown in FIG. Each sample is placed in the sample receiving sections 51_1 and 51_2. Except for this point, the measurement of the emitted light from the sample is the same as in the case of the sample container 20 shown in FIGS. 1 to 3, and the description of the method of measuring the weak light using the sample container 50 shown in FIG. Omitted.

FIG. 8 is a sectional view of the calibration jig. The calibration jig 60 is arranged in the light-shielded sample chamber instead of the sample container 20 and the sample container 50 shown in FIGS. The calibration jig 60 receives the respective ends of two optical fibers (not shown) (here, the ends of these two optical fibers correspond to the two light emitters according to the present invention). Light receiving units 61_1, 6
1_2 is formed. In addition, the calibration jig 60 also has an inlet 6 for the constant temperature circulating water, like the sample containers 20 and 50.
6, an internal flow path 67, and an outlet (not shown) are formed so that the calibration jig 60 is maintained at a constant temperature during calibration.

The calibration jig 60 has two receiving portions 61_
The light-shielding sample chamber 11 is used instead of the sample containers 20 and 50 in a state where the respective end portions of the two optical fibers are received in the optical fiber 1, 61_2.
And from each tip of the two optical fibers,
The light corresponding to the measuring light or the background light is emitted, and the light receiving element 3
By receiving light at 1_1 and 31_2, the light receiving circuit 30
Is calibrated.

As described above, in the present embodiment, the light receiving circuit 30 is calibrated by the calibration jig 60 and the two types of sample containers 2
0,50, in vitro and in vivo
Weak light measurements can be made both with the system. Further, in the present embodiment, as described above, the optical noise and the electrical noise are thoroughly suppressed, and therefore, it is possible to measure the extremely weak light with high accuracy.

In the above embodiment, in each of the sample container 20 shown in FIGS. 1 to 3 and the sample container 50 shown in FIG. 7, each of the exit windows 22_1, 22_2;
Concentrating quartz lenses 23_1, 23_2; 53 at 2_2
_1 and 53_2 are provided, but these quartz lenses 23_1 and 23_2 for condensing light; 53_1 and 53_2 may not necessarily be provided. The reason is that the thickness of the quartz lens becomes close to 6 mm, so that the distance between the sample and the light receiving element increases, and that the light emitted from the sample has a random traveling direction and has a light collecting function. Does not improve the light-gathering properties, so the quartz lenses 23_1, 23
_2; 53_1 and 53_2 are removed, and each emission window 22_
This is because the optical coupling efficiency can be improved by making the thickness of the sample and the light receiving element as close as possible by reducing the thickness of 1,2_2, 52_1 and 52_2. Alternatively, FIG.
-Quartz lenses 23_1, 23_ having the shapes shown in FIGS.
2: Each of the exit windows may be provided with a Fresnel lens that requires only a small wall pressure in place of 53_1 and 53_2.

Next, another embodiment of the weak light measurement system of the present invention will be described. FIG. 9 is a diagram showing the entire configuration including the sample supply device provided in the weak light measurement system of the present invention. As shown in FIG. 9, this weak light measurement system includes (1) an emission window 4 for emitting light emitted from a sample.
Two sample receiving portions 421 provided with 22_1 and 422_2
_1, 421_2 and optical filters 415_1, 415_2 selectively transmitting light emitted from the respective exit windows, a light-shielding sample chamber 411 in which a sample container 420 is exchangeably arranged, and sample receiving portions 421_1, 421_2. Light-transmitting windows 413_1 and 413_1 that transmit light emitted from the respective emission windows
Two light receiving elements 431_1 and 431_2 for receiving each light transmitted through 13_2 and obtaining respective light receiving signals, and an amplifier 43 for amplifying a difference between light receiving signals from these two light receiving elements.
Light-shielding light-receiving chamber 41 in which the light-receiving circuit 430 including
(2) the sample container 42
A sample supply tank 470 in which the sample supplied to the sample supply tank 0 is stored;
(3) A waste liquid receiving tank 480 for receiving the waste liquid from the sample container 420, (4) The difference between the height of the sample liquid in the sample supply tank 470 and the height of the waste liquid in the waste liquid receiving tank 480 is freely adjusted. A liquid level height difference adjusting means 490 and (5) a sample quantitative supply device 500 having a micropump 530 provided in the middle of a pipe 510a for introducing a sample from the sample supply tank 470 to the sample container 420 are provided.

FIG. 10 is a partially detailed view of the sample quantitative supply apparatus shown in FIG. As shown in FIGS. 9 and 10, the sample quantitative supply device 500 is provided with a sample in the same direction at a position close to each other in a pipe 510 a for introducing a sample from the sample supply tank 470 to the sample container 420. Two check valves 531a, 531b, 531a to allow flow
And a check pump 531b, a micro pump 530 having a piston 520 for flowing a sample into a pipe 512 branched from a pipe 511 and flowing out of the sample from the pipe 512, and a gas for driving the piston 520. A drive type actuator 540 is provided.

The check valves 531a and 531b are respectively
Ruby balls 532a, 532b and 532 of small diameter
a, 532b, conical surfaces 533a, 533b, which are valve seats,
Pipe line 534 opened at the center of conical surfaces 533a, 533b
a, 534b and the ruby balls 532a, 532b and the conical surfaces 533a, 533b. Chemical-resistant springs 535a, 535b for holding the ruby balls 532a, 532b at positions such that a gap allowing the flow of the sample is maintained. It has.

In this weak light measurement system, the difference ΔH between the height of the sample liquid in the sample supply tank 470 and the height of the waste liquid in the waste liquid receiving tank 480 is adjusted by the liquid level difference adjusting means 490.
Is configured to be freely adjustable. As described above, the ruby balls 532a, 532b and the conical surfaces 533a, 533b
There is a gap between the sample and the sample that allows the sample to flow,
By making the height of the sample liquid in the sample supply tank 470 higher than the height of the waste liquid in the waste liquid receiving tank 480 by the liquid level difference adjusting means 490, the sample is supplied by the siphon principle without operating the piston 520. The sample in the tank 470 can be continuously supplied into the sample container 420.
At the same time, the waste liquid in the sample container 420 is naturally discharged into the waste liquid receiving tank 480.

In the standby mode, that is, when the flow of the sample is to be stopped, the height of the waste liquid in the waste liquid receiving tank 480 is set to be 40 times higher than the height of the sample liquid in the sample supply tank 470.
By increasing the height by about cm to 50 cm, the flow of the sample based on the siphon principle can be stopped. At this time, the ruby spheres 532a and 532b each have a conical surface 53
3a, 533b will be blocked because it is pressed against
The waste liquid in the waste liquid receiving tank 480 does not flow back into the sample container 420.

When the reciprocating motion of the piston 520 is started by operating the actuator 540, when the piston 520 moves to the right side in the drawing, the pressure in the pipe line 512 becomes negative, and the sample in the sample supply tank 470 is removed from the pipe. From the channel 534a, through the gap between the ruby ball 532a and the conical surface 533a, the line 5
11 flows into. At this time, the ruby ball 532b is pressed against the conical surface 533b, so that the sample from the sample container 420 does not flow back into the conduit 511. Piston 52
When 0 moves to the left side in the drawing, the inside of the pipe 512 is pressurized, and the sample in the pipe 511 passes through the gap between the ruby ball 532b and the conical surface 533b, and the pipe 534b and the pipe 51 are moved.
Ob is supplied to the sample container 420. At this time, since the ruby ball 532a is pressed against the conical surface 533a, the sample in the pipeline 511 does not flow backward to the sample supply tank 470.

When the piston 520 is operated, the liquid level difference ΔH is changed by the liquid level difference adjusting means 490 to adjust the amount of sample supplied from the sample supply tank 470 to the sample container 420. can do.

[0050]

As described above, according to the present invention,
Highly accurate weak light measurement or extremely weak light measurement can be performed.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view from the front showing an embodiment of a weak light measurement device of the present invention in a state in which an embodiment of a sample container of the present invention is disposed inside.

FIG. 2 is a schematic cross-sectional view showing one embodiment of the weak light measuring device of the present invention in a state where an embodiment of the sample container of the present invention is disposed inside.

FIG. 3 is a schematic cross-sectional view of an embodiment of the weak light measuring device of the present invention viewed from above, with one embodiment of the sample container of the present invention disposed therein.

FIG. 4 is a sectional view showing a second embodiment of the weak light measuring instrument according to the present invention.

FIG. 5 is a cross-sectional view showing a weak light measuring device according to a third embodiment of the present invention.

FIG. 6 is a cross-sectional view illustrating a weak light measuring device according to a fourth embodiment of the present invention.

FIG. 7 is a diagram showing another type of sample container which is disposed in the light-shielded sample chamber so as to be interchangeable with the sample containers shown in FIGS.

FIG. 8 is a sectional view of a calibration jig.

FIG. 9 is a diagram showing an entire configuration including a sample supply device provided in the weak light measurement system of the present invention.

FIG. 10 is a partially detailed view of the sample quantitative supply device shown in FIG. 9;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Weak light measuring device 11 Shielded sample chamber 12 Shielded light receiving chamber 13 Translucent window 14 Door 15_1, 15_2 Optical filter 20 Sample container 21_1, 21_2 Sample receiving chamber 22_1, 22_2 Emission window 23_1, 23_2 Quartz lens 24_1a, 24_1b, 24_1c; , 2
4_2b, 24_2c Solution inlet 25_1, 25_2 Solution outlet 26 Inlet 27 Internal flow path 28 Outlet 30 Light receiving circuit 31_1, 31_2 Light receiving element 32 Differential amplifier 40 Ultra high-speed dispenser 41_1a, 41_1b, 41_1c; 41_2a, 4
1_2b, 41_2c Syringe 50 Sample Container 51_1, 51_2 Sample Receptor 51_1a, 51_2a Side 53_1, 53_2 Quartz Lens 56 Inflow 57 Internal Flow Path 59 Lid 60 Calibration Jig 61_1, 61_2 Receptor 66 Inflow 67 Chopper 72 Chopper 72 Driving unit 100 Measurement light 101_1, 101_2 Background light 110, 210, 310 Weak light measurement device 111, 211, 311 Shielded sample chamber 112, 212, 312 Shielded light receiving chamber 115, 215_1, 215_2 Optical filter 120 Sample container 121_1, 121_2, 221_1 , 221_2 Sample receiving section 122_1, 122_2, 222_1, 222_2 Outgoing window 130 Light receiving circuit 131_1, 131_2, 331_1, 331_2 Light receiving element 132 Differential amplifier 213_ , 213_2 Transmissive window 410 Low light measuring device 411 Shielded sample chamber 412 Shielded light receiving chamber 413_1, 413_2 Translucent windows 415_1, 415_2 Optical filter 420 Sample container 421_1, 421_2 Sample receiving part 422_1, 422_2 Outgoing window 431_431 Light receiving circuit 431_431 Light receiving element 432 Amplifier 470 Sample supply tank 480 Waste liquid receiving tank 490 Liquid level difference adjusting means 500 Sample quantitative supply device 510a, 510b, 511, 512, 534a, 53
4b Pipe 520 Piston 530 Micropump 531a, 531b Check valve 532a, 532b Ruby ball 533a, 533b Conical surface 535a, 535b Spring 540 Actuator

Claims (15)

[Claims] 1. A sample receiving section having a sample receiving section for receiving a sample and having an output window for emitting light emitted from the received sample, wherein the output windows of each sample receiving section are arranged on the same plane and are identical. A light-shielding sample chamber in which two sample containers provided so as to face each other are detachably disposed such that emission windows of these two sample receiving portions face downward, and a sample container disposed in the light-shielding sample chamber. Are formed at the lower part of the light-shielding sample chamber with a light-transmitting member made of a light-transmitting member that transmits light emitted downward from the two light-emitting windows, and are emitted from the two light-emitting windows and transmitted through the light-transmitting windows. A light receiving circuit including two light receiving elements arranged with their light receiving surfaces facing upward and an amplifier for amplifying the difference between these two light receiving signals, for receiving each of the received lights to obtain respective light receiving signals, is arranged. Equipped with a shading light receiving chamber And a weak light measuring device. 2. The weak light measuring instrument according to claim 1, wherein the light transmitting member constituting the light transmitting window is formed with an optical filter that selectively transmits light having a desired wavelength. 3. A front face of a light receiving surface of the two light receiving elements,
2. The weak light measuring device according to claim 1, further comprising an optical filter that selectively transmits light having a desired wavelength. 4. An optical system according to claim 1, further comprising: two optical filters provided independently of each other in correspondence with each of the exit windows, between the exit windows and the translucent windows, respectively. Corresponding to each of the two exit windows,
The weak light measuring device according to claim 1, comprising two translucent windows provided independently of each other. 5. A chopper for chopping light incident on these two light receiving elements with a predetermined phase relationship with each other, in front of the two light receiving elements in the light-shielded light receiving chamber. 2. The weak light measuring device according to 1. 6. A first sample receiving portion having an emission window for receiving a sample therein and emitting light emitted from the received sample, and an emission window for receiving light therein and emitting light emitted from the received sample. And a second sample receiving portion arranged side by side with the first sample receiving portion so that the exit window is arranged on the same plane as the exit window of the first sample receiving portion and faces in the same direction. A sample container, comprising: 7. An inner wall of the first and second sample receiving portions, except for an emission window of each of the first and second sample receiving portions, is received by each of the first and second sample receiving portions. 7. The sample container according to claim 6, further comprising a reflecting surface for reflecting light emitted from each sample toward the emission windows of the first and second sample receiving portions. 8. A light-collecting member for condensing each light emitted from each sample received in the first and second sample receiving portions, in each of the emission windows of the first and second sample receiving portions. 7. The sample container according to claim 6, wherein: 9. A plurality of solution inlets corresponding to the first and second sample receiving portions, respectively, and the solutions flowing from the plurality of solution inlets are mixed to form the first and second samples. 7. The apparatus according to claim 6, further comprising: a solution inflow path for flowing into each of the receiving sections; and a solution outflow path for flowing out each of the solutions received in each of the first and second sample receiving sections. Sample container. 10. The sample container according to claim 6, further comprising a detachable lid that opens a side of the first and second sample receiving portions that faces the emission window. 11. The sample container according to claim 4, further comprising means for maintaining said sample container at a predetermined temperature. 12. A first sample receiving portion having an emission window for receiving a sample therein and emitting light emitted from the received sample, and an emission window for receiving the sample therein and emitting light emitted from the received sample. A second sample receiving section arranged alongside the first sample receiving section such that the exit window is arranged on the same plane as the exit window of the first sample receiving section and faces in the same direction; and A plurality of solution inlets respectively corresponding to the first and second sample receiving portions;
Solution inflow paths into which the solutions respectively flowing from the plurality of solution inlets are mixed and flow into the first and second sample receiving portions, respectively, and the solutions received into the first and second sample receiving portions, respectively. A first sample container provided with a solution flow path composed of solution outflow paths for allowing the sample to flow out, and a third sample receiving portion provided with an emission window for receiving a sample therein and emitting light emitted from the received sample. An emission window for receiving a sample therein and emitting light emitted from the received sample, the emission window being arranged on the same plane as the emission window of the third sample receiving portion and facing in the same direction. A fourth sample receiving portion arranged side by side with the sample receiving portion of
A second sample container having a detachable lid that opens a side of the third and fourth sample receiving portions facing the emission window, wherein the first and second sample containers are exchangeable. A light-shielding sample chamber arranged with the emission window facing downward, and a light transmitting member for transmitting light emitted downward from two emission windows of the first and second sample containers arranged in the light-shielding sample chamber. A light-receiving surface formed at a lower portion of the light-shielding sample chamber with a light-transmitting window formed therebetween and receiving each light emitted from each of the two emission surfaces and transmitted through the light-transmitting window to obtain each light-receiving signal; Characterized by comprising a weak light measuring device provided with a light-shielded light-receiving chamber in which a light-receiving circuit including two light-receiving elements arranged with the light-receiving element facing upward and an amplifier for amplifying the difference between these two light-receiving signals is arranged. Weak light measurement system. 13. A calibrating jig for receiving two illuminants emitting light toward each of the two light receiving elements, which is disposed in the light-shielded sample chamber so as to be interchangeable with the first and second sample containers. The low-light-level measuring system according to claim 12, comprising: 14. A sample supply tank for storing a sample to be supplied to the sample container, a waste liquid receiving tank for receiving a waste liquid from the sample container, a height of a sample liquid surface in the sample supply tank, and the waste liquid receiving tank. 13. The weak light measuring system according to claim 12, further comprising a liquid level height difference adjusting means for freely adjusting a difference between the liquid level and the liquid level in the liquid. 15. A two-way check valve for allowing a sample to flow in the same direction at a position close to each other in a pipe for introducing a sample into the sample container, and a pipe connecting the two check valves. 13. The weak light measurement system according to claim 12, further comprising a sample quantitative supply device having a piston for allowing a sample to flow into and out of the branched pipe.