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GB2055200A - Enhancement of the sensitivity of bioluminescent and chemiluminescent assays with enzymatic cycling - Google Patents

Enhancement of the sensitivity of bioluminescent and chemiluminescent assays with enzymatic cycling Download PDF

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GB2055200A
GB2055200A GB8023995A GB8023995A GB2055200A GB 2055200 A GB2055200 A GB 2055200A GB 8023995 A GB8023995 A GB 8023995A GB 8023995 A GB8023995 A GB 8023995A GB 2055200 A GB2055200 A GB 2055200A
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Abstract

Bioluminescent and chemiluminescent assays coupled with enzymatic cycling systems greatly increase the versatility and sensitivity of substrate and enzyme assays based on enzymatic cycling principle. Besides the normal pyridine nucleotide cycling system it is possible to use the adenine nucleotide system when the produced substrates are measured by the bioluminescent assay of ATP. Utilizing the bioluminescent assays of NADH, NADPH or ATP, or the chemiluminescent assay of H2O2 or O2 it is possible to measure more substrates produced in the enzymatic cycling systems than has been possible by spectrophotometry or fluorometry. The sensitivity of the measurement with the luminescent assay systems are 2 to 3 orders of magnitude higher than with fluorometry.

Description

SPECIFICATION Enhancement of the sensitivity of bioluminescent and chemiluminescent assays with enzymatic cycling Enzymatic cycling is a method of a chemical amplification of an analyte (W. J. Blaedel and R. G.
Boguslaski; Anal. Chem. 50:1026-1032, 1 978). Enzymatic cycling applies alternate oxidating and reduction of pyridine nucleotides by two specific enzymes in a cycling fashion (T. Kato, S. J. Berger, J. A.
Cater and D. H. Lowry; Anal. Biochem. 53: 86-97, 1973). During this enzymatic cycling one molecule is accumulated during each cycle of the pyridine nucleoxide. This type of system can turn over from 2,000 to 30,000 times per hour multiplying the quantity the analyte by this high factor. Enzymatic cycling has been applied to increase the sensitivity of spectrophotometric and fluorometric substrate and enzyme assays.
Fig. 1. schematically shows the enzymatic cycling applying nicotinamide-adenine dinucleotide in oxidated form (NAD+) and reduced form (NADH) and alcohol dehydrogenase enzyme (EC 1.1.1.1) and malic dehydrogenase enzyme (EC 1.1.1.37) to produce aldehyde and malate substrates. The turnover is over 30.000 times per hour and the number of actual molecules produced is proportional to the concentration of NAD+ or NADH in the sample.
-If the enzymes are pure, there are no side reactions utilizing the pyridine nucleotides (NAD and NADH), the concentration of the pyridine nucleotides in the sample stays constant throughout the cycling procedure. Amplification factor is determined by the turnover rates of the enzymes and the final concentration of accumulated substrate is proportional to the stoichiometric amount of pyridine nucleotide in the sample.
Useful indicator reactions for measuring the produced substrates in the system, shown in Figure 1., are: 1. Malate + NADPH + malic
enzyme pyruvate + CO2 + NADP + H+ or 2. Malate + NAD + malic
dehydrogenase oxalacetate + NADH + The measurement of malate is made either spectrophotometrically or fluorometrically on the basis of absorption or fluorescence of pyridine nucleotides, respectively.
In theory it should also be possible to measure oxalacetate produced in the cycling reaction in Figure 1., but when the cycling is stopped by heating samples to 100 C, oxalacetate breaks down.
The procedure of enzymatic cycling with pyridine nucleotides of the system in Figure 1. is as following: For the cycling reagent there is prepared a mixture of controlled quantities of alcohol dehydrogenase (20--200 Mg/ml) and malic dehydrogenase (0.5-10 Iss/ml) and non-limiting concentrations of ethanol (200-500 mM) and oxalacetate (1-2 mM) in 100 mM Tris-HCI (pH 8.0) buffer containing 2 mM mercapto-ethanol and 0.02% bovine serum albumin.
1. 10 yI sample containing NAD is added to 100,us of cycling reagent at OOC. Blanks and standards are prepared similarly. Everything should be pipetted as fast as possible to avoid differences in the reaction times.
2. Samples are incubated for 60 minutes at +250C.
3. Samples are heated for 3 minutes at 1000C.
4. Indicator reagent is added and incubated 3-20 minutes to convert malate to pyruvate (reaction 1) or to oxalacetate (reaction 2) and the fluorescence of produced NADP or NADH, respectively, is measured.
The disadvantages of the spectrophotometric and fluorometric measurements of the concentration of substrates produced in the enzymatic cycling are that the lower limit of fluorometric measurement is with one cycling in the order of 1 0-14 moles and with two cyclings 1 0-15 moles. These limits are caused by the sensitivity of fluorescence principle itself and the blank values of the reagent system. Sensitivity of spectrophotometry is even less. Both these methods also suffer from non-specific absorption (spectrophotometry) and fluorescence of other substrates than the measured product (fluorometry).
Bioluminescence assays are of two to three orders magnitude more sensitive and also more specific to the measured substance than either spectrophotometry or fluorometry. The practical sensitivity limit of firefly bioluminescence is at 10-16 moles and photobacterial bioluminescence 10-'5 moles (Wettermark, G., H. Stymne, S. E. Brolin and B. Petterson. Anal. Biochem. 63 :293-307, 1975; Haggerty, C., E. Jablonski, L. Star and DeLuca. Anal. Biochem. 88:162-173, 1978). Thus the direct measurement is already more sensitive than the enzymatic cycling method using fluorometry.
However, when enzymatic cycling is applied, it is possible to get down to 1 0-1S1 0-20 moles of a substrate.
Bioluminescent assay coupled with the enzymatic cycling offers great versatility as it is possible to apply both adenine and pyridine nucleotides for the cycling process as compared to conventional methods of applying the pyridine nucleotides only.
Bioluminescent assays of ATP with firefly system and pyridine nucleotides (NADH, NADPH) with bacterial system are known per se (M. DeLuca: Bioluminescence and Chemiluminescence, Methods-in Enzymology, Vol. 48, Academic Press, New York, N.Y., 1978). The utilization of enzymatic cycling in connection with bioluminescent assays is not known before. The need to further improve the sensitivity of bioluminescent assays with enzymatic cycling applies to measurement of substrates and enzymes with low cost instrumentation that do not offer the high photon sensitivity, or with sensitive instruments to allow the detection of single bacteria or measurement of enzyme and substrates in single cellular level as well as for immuno-assays.
Exampies of enzymatic cycling for bioluminescent assays are as following: A. Amplification of ATP (adenosine triphosphatej concentration. ATP concentration in the sample can be amplified several orders of magnitude by an enzymatic cycling system illustrated in Figure 2.
The amplification of ATP is accomplished through an enzymatic cycling with adenosine monophosphate (AMP) and phosphoenol pyruvate (PEP) as substrates and adenylate kinase (ATP: AMP phosphotransferase EC 2.7.4.3) and pyruvate kinase (ATP: pyruvate 2-O-ph;osphotransferase EC 2.7.1.40) as enzymes. With each turnover one molecule of ATP is produced in excess by pyruvate kinase 2 ADP + 2 PEP PK
pyruvate + 2 ATP.
-In 60 minutes the original ATP concentration can be amplified 1.000 to 10.000 times. The reaction produces one extra molecule of ATP for each cycle and the produced ATP is directly proportional to the original concentration of ATP in the sample and the number of enzyme cycles. Produced ATP is measured with the firefly bioluminescent system.
The inhibition of high concentration of AMP in the firefly reaction can be eliminated by converting AMP to other metabolites with enzymes, e.g. with AMP deaminase.
Procedure for the amplification of ATP concentration in the sample: - A 10-100 yI sample containing 1 0-1a1 0-12 moles of ATP is pipetted to -100-1,000 yI, cycling reagent containing 50-500 units/ml of adenylate kinase and 5-50 units/ml pyruvate kinase, and 1-5 mM AMP (adenosine monophosphate) and 1-5 mM PEP-(phosphonol pyruvate) in 0.1 M Tris-HCI or phosphate buffer, pH 7.0-8.0 containing 5-20 mM Mg+±ion and 5-20 mM K±ion and 4 mM EDTA. Samples, blanks and ATP standards-are pipetted within 5 minutes and reagents and samples kept cool at +OOC during the pipetting to lower the reaction rate during pipetting.
- Samples are incubated at 25-3O0C for 30 or 60 minutes.
-The cyc!ing reaction is stopped by heating the samples to 1 000C for 3 minutes.
-Accumulated ATP is measured with the firefly bioluminescent assay as following: An aliquote of sample solution 10-1,000 yI, but preferably 100 pl is taken and added to 10-100 yI firefly luciferin-luciferase reagent, but preferably 100 ,al containing 0.01-2 y9, but preferably 0.1--0.5 ug luciferase and 0.01-1 mM, but preferably 0.1-0.5 mM luciferin in a biochemical buffer having 5-50 mM magnesium ion, preferably 7-10 mM and pH between 7-8.5, but preferably between 7.4-7.8, and the emitted light intensity measured as a peak or as an integrated value over a preset time. The value of light intensity is converted to ATP by comparing it to the light intensity produced by a known ATP standard, measured similarly.
-The original ATP concentration in the samples is calculated by comparing the value after cycling to those of standards treated similarly and after substrating blank values from both. Enzymes have to be purified and free from contaminating enzymes that could cause side reactions. Substrates (AMP and PEP) should not have ADP (adenosine diphosphate) or AMP contamination.
B. Amplification of a substrate through ATP-ADP conversion is enzymatic cycling: An analogous method to conventional enzymatic cycling (Figure 1.) is illustrated in Figure 3. by the amplification of creatine phosphate (CP) with creatine and PEP as substrate and ATP in sample with creatine kinase (ATP: creatine N-phosphotransferase EC 2.7.3.2) and pyruvate kinase. One molecule of creatine phosphate (CP) and pyruvate are produced during each turnover of the ATP-ADP system. After stopping the cycling by heating, creatine phosphate can be converted to creatine and ATP in the indicator reaction during a 5-1 5 minute incubation.
Creatininase is used in the indicator reagent to pull the CP + ADF CK
ATP + creatine reaction to completion. The quantity of CP produced is proportional to the quantity of ATP in the sample. ATP produced in the indicator reaction is measured with the firefly bioluminescent assay.
C. Amplification of a substrate through pyridine nucleotide oxido-reduction in enzymatic cycling: It is possible to produce substrates that can be measured with the bioluminescent assay of ATP using a NADH-NAD or NADPH-NADP cycling system. Figure 4. shows an example for production of glycerol3-phosphate (G-3-P) using NAD±NADH cycling, dihydroxyaceton phosphate (DAP) and lactate as substrates and glycerin-3-phosphate dehydrogenase (SM-glycerol-3 phosphate: NAD 2-oxidereductase EC 1.1.1.8) and lactate dehydrogenase (D-lactate: NAD oxidoreductase EC 1.1.1.28) as cycling enzymes. Produced glycerol-3-phosphate is converted with glycerokinase (ATP: glycerol-3 phosphotransferase EC 2.7.1.30) and ADP to ATP to be measured with the firefly bioluminescent assay.
D. Amplification of a substrate with pyridine nucleotide oxidoreduction for measurement with bacterial bioluminescence: Figure 5. gives an example of an enzymatic cycling system where 6-phospho-gluconate and glutamate are produced with NADP-NADPH oxidoreduction system.
6-P-gluconate is converted to ribulose-5-phosphate and NADPH. NADP concentration in the sample is amplified with glucose-6-phosphate dehydrogenase (D-glucose-6-phosphate: NADP l-oxidoreductase (EC 1.1.1.49) and glutamate dehydrogenase (L-glutamate: NAD(P) oxidoreductase EC 1.4.1.3) using glucose-6-phosphate, a-ketoglutarate and ammonia as substrates. Produced 6-phosphoglucomate (6-P-gluconate) is converted to a stoechiometric quantity of NADPH with NADP and 6-phosphogluconate dehydrogenase (6-phospho-D-gluconate: NADP 2-oxidoreductase EC 1.1.1.44).
Produced NADPH is measured with bacterial bioluminescence using the system given in Figure 6.
Reduced nicotinamide adenine dinucleotide phosphate (NADPH) is used to reduce flavin mononucleotide (FMN) to FMNH2 by NADPH: FMN oxidoreductase (EC 1.6.99.-) FMNH2 serves a role of the luceferin and reacts with oxygen and a long-chain aldehyde (8-1 6 carbon chain) when catalyzed by luciferase, producing photons in the blue regions of visible light.
Bioluminescence assays of ATP, NADH and NADPH greatly increase the sensitivity and versatility of enzymatic cycling methods for measurements of substrates. The application of ATP-ADP conversion systems allows the use of many of the about 220 ATP-specific enzymes for enzymatic cycling, thus the possibility of measurement of adenylate and other nucleotide phosphates as well as ATP-specific enzymes.
E. Utilization of chemiluminescent assays for measurement of substrates produced in enzymatic cycling: High specificity and sensitivity of certain chemiluminescent assays of hydrogen-peroxide and suporoxide increase the range of substrates measurements in conjunction with enzymatic cycling. This is performed by applying oxidase enzymes which react with a product of an enzymatic cycling system.
In Figure 1. acetaldehyde is one product of the cycling reaction. After stopping the reaction by heating, the following indicator reaction involving an oxidase enzyme can be used to produce hydrogen peroxide: acetaldehyde + H20 - aldehyde
oxidase H2O2 + 1 Produced peroxide is then measured with luminol (5-amino-2.3-dihydrophtalazine-1 .4-dione) in alkaline medium using a first transition series metal as a catalyst:: luminol + 2H2O2 + OH - Fe++
pH 10-12 aminophthalic acid + 3H2O + N2 + photon (R max. 425 nm) With this it is possible to measure down to 10-'0 moles of H202, thus concentration of NAD+ down to 1 0-14 moles can be assayed with chemiiuminescence using enzymatic cycling procedure.
Utilization of both adenylate phosphate and pyridine nucleotides in enzymatic cycling systems increase the versatility of chemical amplification with enzymatic cycling. The sensitivity and versatility of enzymatic cycling technique is further increased by applying bioluminescent and chemiluminescent assays for the measurement of the produced substrates. With fluorometry and enzymatic cycling it is possible to measure pyridine nucleotides down to 1 0-111 0-12 moles with single cycling and down to 10-'5 moles with double cycling. With bioluminescence it is possible to measure pyridine nucleotides down to 10-'4 and adenine nucleotides down to 10-'5 moles with a single cycle.
Chemiluminescence allows the measurement of substrates down to 10-14 moles with single cycle.
With double cycling and utilizing luminescent assays for measurement, it is possible to go down another four orders of magnitude, thus to 10-'8--1 0-'9 moles, if the cycling reagents are highly purified.
Luminescent measurement increases the sensitivity of the enzymatic cycling method up to 2-3 orders of magnitude and increases the number as compared with the conventional spectrophotometric and fluorometric methods.
In practice the enzymatic cycling for measurement of a substrate can be performed by adding to a sample a prepared mixture of other substrates and the enzymes required in the particular cycling system. This means that only one reagent mixture is needed. It is also possible to apply immobilized enzymes for the cycling, in which case only the additional substrates have to be dispensed to the sample after the sample is in contact with the immobilized enzymes.
Enzymatic cycling for amplifying concentration of a substrate for measurement of it with bioluminescent or chemiluminescent assay is simple to perform with ready-made reagent mixtures, and offers a sensitivity limit of more than two orders of magnitude over fluorometric method for the same assays. Application of bioluminescent and chemiluminescent measurement widely increase the choice of enzymatic cycling system because ATP, NADH, NADPH and H202 based reactions can be measured.

Claims (11)

1. A system of utilizing bioluminescent and chemiluminescent assays for measuring substrate concentrations and-enzyme activities in conjunction with different enzymatic cycling systems.
2. A system of claim 1 wherein the enzymatic cycling system is based on the chemical amplification of adenosine triphosphate (ATP) by an ADP-ATP cycling using AMP and PEP as substrates, and adenylate kinase and pyruvate kinase as cycling reagents to produce one extra molecule of ATP with each turnover of the enzyme systems, AMP +ATP adenylate kinase
2 ADP ZADP + PEP pyruvate kinase
2 ATP + pyruvate
3. A system of claim 2 wherein the enzyme system is let to turn over 100--1000 times to increase the original ATP concentration by the same factor during a 0.5-2 hour incubation time.
4. A system of claim 3 wherein the produced ATP is measured with the firefly bioluminescent system.
5. A system of claim 1 wherein the NAD-NADH of NADP-NADPH enzymatic cycling system produces a substrate that can enzymatically converted to ATP.
6. A system of claim 1 wherein an ADP-ATP enzymatic cycling system produces a substrate that enzymatically can be converted to ATP.
7. A system of claim 5, wherein the concentration of produced ATP is measured with the firefly bioluminescent system, and the obtained ATP concentration converted to the concentration of the original concentration of the pyrudine nucleotide of interest.
8. A system of claim 7 wherein the concentration of ATP after enzymatic cycling and enzymatic conversion of the accumulated substrate is measured as ATP with the firefly bioluminescent assay, and that result converted to the original concentration of ATP or ADP in the sample.
9. A system of claim 1 wherein the enzymatic cycling is used to accumulate a substrate that in an enzymatic reaction produces superoxide or peroxide to be measured with chemiluminescence assay.
10. A system of claim 1 wherein an NAD-NADH or NADP-NADPH system produces a substratethat through an enzymatic indicator reaction is converted to NADH or NADPH.
11. A system of claim 10 wherein the concentration of NADH or NADPH is measured with the bacterial bioluminescent reaction.
GB8023995A 1979-07-24 1980-07-22 Luminescent assays with enzymatic cycling enhancement of the sensitivity of bioluminescent and chemi Expired GB2055200B (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049606A1 (en) * 1980-10-02 1982-04-14 Colin Henry Self Detection method, use and diagnostic aid
FR2545504A1 (en) * 1983-04-25 1984-11-09 Toyo Jozo Kk METHOD OF TITRATION USING NAD-SYNTHETASE AND PROCESS FOR PRODUCTION OF ENZYME
FR2547926A1 (en) * 1983-06-27 1984-12-28 Biomerieux Sa Process for assaying oestrogens and androgens by amplification and bioluminescence
DE4011297A1 (en) * 1989-04-06 1990-10-11 Japan Spectroscopic Co MEASURING METHOD AND MEASURING DEVICE FOR ALDEHYDE MEASUREMENT
FR2699930A1 (en) * 1992-12-24 1994-07-01 Kabore Paul Bioluminescent determn of adenosine phosphates
WO1994025619A1 (en) * 1993-04-23 1994-11-10 Celsis Limited Detection of biological material
US6159693A (en) * 1998-03-13 2000-12-12 Promega Corporation Nucleic acid detection
US6235480B1 (en) 1998-03-13 2001-05-22 Promega Corporation Detection of nucleic acid hybrids
US6268146B1 (en) 1998-03-13 2001-07-31 Promega Corporation Analytical methods and materials for nucleic acid detection
US6270973B1 (en) 1998-03-13 2001-08-07 Promega Corporation Multiplex method for nucleic acid detection
US6270974B1 (en) 1998-03-13 2001-08-07 Promega Corporation Exogenous nucleic acid detection
US6277578B1 (en) 1998-03-13 2001-08-21 Promega Corporation Deploymerization method for nucleic acid detection of an amplified nucleic acid target
US6312902B1 (en) 1998-03-13 2001-11-06 Promega Corporation Nucleic acid detection
US6335162B1 (en) 1998-03-13 2002-01-01 Promega Corporation Nucleic acid detection
US6391551B1 (en) 1998-03-13 2002-05-21 Promega Corporation Detection of nucleic acid hybrids
GB2375171A (en) * 2000-12-15 2002-11-06 Lumitech Method for detecting protein kinase activity using a bioluminescence reaction
US6703211B1 (en) 1998-03-13 2004-03-09 Promega Corporation Cellular detection by providing high energy phosphate donor other than ADP to produce ATP
US7090975B2 (en) 1998-03-13 2006-08-15 Promega Corporation Pyrophosphorolysis and incorporation of nucleotide method for nucleic acid detection
CN108872205A (en) * 2018-06-19 2018-11-23 深圳上泰生物工程有限公司 The application of object detection method of content and detection reagent in the detection method
EP4159755A4 (en) * 2020-05-25 2024-07-31 Yokogawa Electric Corporation METHOD FOR DETECTING A TARGET MOLECULE IN A SAMPLE, AND TARGET MOLECULE DETECTION KIT

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0049606A1 (en) * 1980-10-02 1982-04-14 Colin Henry Self Detection method, use and diagnostic aid
FR2545504A1 (en) * 1983-04-25 1984-11-09 Toyo Jozo Kk METHOD OF TITRATION USING NAD-SYNTHETASE AND PROCESS FOR PRODUCTION OF ENZYME
DE3415436A1 (en) * 1983-04-25 1985-05-15 Toyo Jozo K.K., Tagata, Shizuoka ASSAY METHOD USING NAD SYNTHETASE AND A METHOD FOR PRODUCING THE ENZYME
FR2547926A1 (en) * 1983-06-27 1984-12-28 Biomerieux Sa Process for assaying oestrogens and androgens by amplification and bioluminescence
DE4011297A1 (en) * 1989-04-06 1990-10-11 Japan Spectroscopic Co MEASURING METHOD AND MEASURING DEVICE FOR ALDEHYDE MEASUREMENT
DE4011297C2 (en) * 1989-04-06 1998-08-06 Japan Spectroscopic Co Device for collecting and measuring gaseous aldehydes from a gaseous sample
FR2699930A1 (en) * 1992-12-24 1994-07-01 Kabore Paul Bioluminescent determn of adenosine phosphates
WO1994025619A1 (en) * 1993-04-23 1994-11-10 Celsis Limited Detection of biological material
US6043047A (en) * 1993-04-23 2000-03-28 Celsis International, Plc Sample-collecting and assay device for use in the detection of biological material
US6277578B1 (en) 1998-03-13 2001-08-21 Promega Corporation Deploymerization method for nucleic acid detection of an amplified nucleic acid target
US6391551B1 (en) 1998-03-13 2002-05-21 Promega Corporation Detection of nucleic acid hybrids
US6268146B1 (en) 1998-03-13 2001-07-31 Promega Corporation Analytical methods and materials for nucleic acid detection
US6270973B1 (en) 1998-03-13 2001-08-07 Promega Corporation Multiplex method for nucleic acid detection
US6270974B1 (en) 1998-03-13 2001-08-07 Promega Corporation Exogenous nucleic acid detection
US6159693A (en) * 1998-03-13 2000-12-12 Promega Corporation Nucleic acid detection
US6312902B1 (en) 1998-03-13 2001-11-06 Promega Corporation Nucleic acid detection
US6335162B1 (en) 1998-03-13 2002-01-01 Promega Corporation Nucleic acid detection
US6379898B2 (en) 1998-03-13 2002-04-30 John W. Shultz Nucleic acid detection
US6235480B1 (en) 1998-03-13 2001-05-22 Promega Corporation Detection of nucleic acid hybrids
US7090975B2 (en) 1998-03-13 2006-08-15 Promega Corporation Pyrophosphorolysis and incorporation of nucleotide method for nucleic acid detection
US6730479B2 (en) 1998-03-13 2004-05-04 Promega Corporation Detection of nucleic acid hybrids
US6703211B1 (en) 1998-03-13 2004-03-09 Promega Corporation Cellular detection by providing high energy phosphate donor other than ADP to produce ATP
US6653078B2 (en) 1998-03-13 2003-11-25 Promega Corporation Multiplex method for nucleic acid detection
US6599711B2 (en) 2000-12-15 2003-07-29 Lumitech (Uk) Limited Methods and kits for detecting protein kinases
GB2375171B (en) * 2000-12-15 2003-03-12 Lumitech Methods and kits for detecting protein kinases
US6911319B2 (en) 2000-12-15 2005-06-28 Lumitech (Uk) Limited Methods and kits for detecting protein kinases
GB2375171A (en) * 2000-12-15 2002-11-06 Lumitech Method for detecting protein kinase activity using a bioluminescence reaction
CN108872205A (en) * 2018-06-19 2018-11-23 深圳上泰生物工程有限公司 The application of object detection method of content and detection reagent in the detection method
EP4159755A4 (en) * 2020-05-25 2024-07-31 Yokogawa Electric Corporation METHOD FOR DETECTING A TARGET MOLECULE IN A SAMPLE, AND TARGET MOLECULE DETECTION KIT

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