KR20040018740A - method of analyzing a sample material and apparatus of performing the same - Google Patents

Abstract

PURPOSE: A method for analyzing a sample and its apparatus are provided, to measure the concentration of a metal ion, a biomaterial or an environmental pollutant precisely by the reaction due to the surface diffusion. CONSTITUTION: The method comprises the steps of (S22) preparing a reagent showing chemiluminescence in a cell; (S24) preparing a sample in a tube; (S26) dropping the sample prepared in the tube into the reagent of the cell to diffuse the sample onto the surface of the reagent; and (S34) measuring the intensity of the light emitted by the reaction due to the surface diffusion, thereby (S36) obtaining the concentration of the material to be analyzed in the sample. Preferably the reagent comprises luminol, and comprises further hydrogen peroxide, a periodate salt or their mixture.

Description

Method of analyzing a sample material and apparatus of performing the same

The present invention relates to a method for analyzing a sample material and a device for performing the same, and more particularly, to a method for quantitatively analyzing a sample material such as trace metal ion materials, biomaterials, environmentally harmful substances or other compounds, and the like. It relates to an apparatus for performing this.

In general, the analysis of the sample material is accomplished by spectroscopy such as atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), inductively coupled plasma-mass spectroscopy (ICP-MS), and the like. However, the spectroscopy has a problem of stability because it is expensive to maintain and uses a flame or a high temperature plasma. Moreover, the spectroscopy has a problem that the device itself is expensive and its operation is difficult. Thus, recent analysis of sample materials utilizes emission spectroscopy with excellent sensitivity and low detection limits. Among the emission spectroscopic methods, the most widely used method is a chemical luminescence (chemiluminescence) method.

In addition, the luminescence assay is suitable for quantitative analysis of not only metal ion materials such as Fe (II), Cu (II), Co (II), Cr (III), etc., but also biomaterials, environmentally harmful substances or other compounds. Can be applied. For example, the luminescence assay may be applied to a sample material of a polyalcohol family such as adrenaline or the like reacting with luminol.

Conventional apparatus for achieving the chemical luminescence assay has a container including an air inlet tube, two drug inlet tubes and a drug outlet tube. In the assay using the device, a reagent containing luminol and hydrogen peroxide and a sample containing the sample material are introduced into each of the two drug introduction tubes. Then, air is introduced into the air introduction pipe. The reagent and the sample drug are mixed while moving inside the container by the force applied by the introduction of the chemical and the force applied by the introduction of air. And light is emitted by reacting by the said mixing. Accordingly, the concentration of the sample material is obtained by measuring the intensity of the emitted light. And, the drug is completed the reaction is discharged through the drug discharge pipe.

However, the chemical luminescence assay by the above apparatus and method has the following problems. First, since the container is cylindrical and larger in diameter than the chemical introduction tube, perfect mixing of the medicine, that is, the reagent and the sample, is not achieved. Secondly, continuous analysis results in a memory effect in which the drug is introduced continuously into the same container so that the drug introduced first affects the intensity of light emitted from the drug introduced later. Third, by injecting air, light scattering by the air occurs, affecting the stability and reproducibility of the measurement.

Thus, the method by the apparatus and method is applicable to the apparatus and method for qualitative analysis, but is not suitable for quantitative analysis for accurately measuring the concentration of the sample material.

Accordingly, recently, a method and apparatus for solving the above problems are under research and development. An example of a method and apparatus for a chemical luminescence assay presented as part of the research and development is disclosed in Korean Patent Application No. 1999-56755.

According to Korean Patent Application No. 1999-56755, quantitative analysis of the metal ions is possible. However, the analysis according to the Korean Patent Application No. 1999-56755 has a disadvantage in that the consumption of drugs used in the analysis is high. This is because the drug must be continuously filled in the mixing path by extending the path in which the medicine is mixed in order to extend the time for mixing the medicine. In addition, the ppm unit can be accurately analyzed, but does not mention the analysis of ppb to ppt unit. Thus, it is not suitable for quantitative analysis of sample materials such as biomaterials, environmentally harmful substances or other compounds, which are mostly measured in ppb to ppt units. In addition, since the reaction route is extended, it takes a lot of analysis time.

Therefore, recently, there is a need for a method and apparatus for maximizing consumption of a drug including a reagent and a sample, accurately performing ppb to ppt analysis, and minimizing analysis time.

It is a first object of the present invention to provide a method for analyzing a sample material through a reaction by surface diffusion.

It is a second object of the present invention to provide an apparatus for analyzing a sample material through a reaction by surface diffusion.

1 is a schematic diagram illustrating a device for analyzing a sample material according to an embodiment of the present invention.

2 is a flowchart illustrating a method of analyzing a sample material according to an embodiment of the present invention.

3 is a schematic configuration diagram showing a state in which a sample is surface-diffused when analyzing a sample material by the method of the present invention.

Figure 4 is a graph showing the result of measuring the mass of the sample dropped intermittently when using the temperature control unit of the present invention.

5 is a graph showing a result of measuring the mass of a sample dropped by free fall according to the present invention.

6 is a graph showing the light transmittance according to the material of the window of the cell of the present invention.

7 shows a standard calibration curve of the standard Fe (II) solution of the present invention.

8 is a graph showing the results of measuring the ion concentration of Fe (II) according to the method of the present invention.

9 shows a standard calibration curve of the standard Cu (II) solution of the present invention.

10 is a graph showing the results of measuring the ion concentration of Cu (II) according to the method of the present invention.

11 shows a standard calibration curve of the standard Cr (III) solution of the present invention.

12 is a graph showing the results of measuring the ion concentration of Cr (III) according to the method of the present invention.

Figure 13 shows a standard calibration curve of a standard Fe solution comprising the DHF of the present invention.

14 is a graph showing the results of measuring the ion concentration of Fe containing DHF according to the method of the present invention.

15 shows a standard calibration curve of a standard Cu solution comprising the DHF of the present invention.

16 is a graph showing the results of measuring the ion concentration of Cu containing DHF according to the method of the present invention.

17 is a graph showing the results of measuring the concentration of adrenaline according to the method of the present invention.

The method of the present invention for achieving the first object comprises the steps of providing a reagent in which a chemiluminescence occurs in a cell, preparing a sample containing a sample material to be analyzed in a tube, and Dropping the sample onto the reagent in the cell to diffuse the sample onto the surface of the reagent; And determining the concentration of the sample material by measuring the intensity of light emitted through the reaction by the surface diffusion.

An apparatus of the present invention for achieving the second object is a cell having a window that allows the surface diffusion to receive the drug, and transmits the light emitted by the reaction of the drug, and the first tube for sucking the drug A dropping portion having a medicine drawn into the first tube and dropped into the cell; And a detector positioned at the bottom of the cell and measuring the concentration of the sample material to be analyzed by measuring the intensity of the emitted light in real time.

According to the method and apparatus, the concentration of the sample material such as metal ion material, bio material, environmentally harmful material or other compound can be obtained more accurately by measuring the light intensity through reaction by surface diffusion. In addition, by using the surface diffusion reaction, it is possible to accurately analyze the ppb to ppt unit. In addition, since surface diffusion is possible with a small amount of chemicals, the consumption of the chemicals can be minimized. In addition, surface diffusion can occur instantaneously, minimizing analysis time.

Hereinafter, the present invention will be described in detail.

1 is a schematic diagram illustrating a device for analyzing a sample material according to an embodiment of the present invention.

Referring to FIG. 1, the analysis device 1 includes a cell 10 containing a medicine and a dropping portion 12 for inhaling the medicine and dropping the inhaled medicine into the cell. Here, as an example of the said chemical agent, a reagent and a sample are mentioned. In addition, the reagent is a drug in which a luminescence reaction, that is, a chemiluminescence phenomenon occurs. The sample contains the sample material to be analyzed. Examples of the sample material include metal ionic materials, biomaterials, environmentally harmful substances, other compounds, and the like. These may be included in the sample alone or two or more may be included in the sample.

The cell 10 is preferably accommodated in a form that allows the surface diffusion when the drug is received. Accordingly, the cell 10 is preferably a cylinder type or a hexahedron type. When the cell 10 is a cylinder type, the diameter of the underside is preferably about 8 to 12 mm. When the cell 10 is a hexahedron type, the height is preferably 3 to 15 mm. In addition, the cell 10 preferably has a similar volume regardless of its type. One surface of the cell 10 has a window 101 for transmitting light emitted by the reaction of the drug. At this time, the portion where the window 101 is installed is preferably the bottom surface, that is, the bottom surface of the cell 10. In addition, each of the cells 10 and the windows 101 is preferably made of optical glass, quartz or optical polymer. At this time, an example of the said optical polymer is PDMS, PMMA, etc. are mentioned. In particular, when measuring a sample that can corrode the cell 10, such as HF, it is preferable to use a cell 10 made of the optical polymer.

The dripping portion 12 has a first pipe 121 for sucking the medicine. Therefore, the medicine may be sucked into the first pipe 121 and the sucked medicine may be dropped into the cell 10. At this time, the first tube 121 of the dropping portion 12 is preferably a capillary tube that can suck the drug by the capillary phenomenon. In addition, the dripping portion 12 includes a second tube 123 connected to the first tube 121. In addition, the dripping portion 12 includes a temperature adjusting unit 125 installed around the second tube 123. The temperature adjusting unit 125 includes a coil 125a surrounding the second pipe 123 and a power applying unit 125b for applying power to the coil 125a. Here, the temperature adjusting unit 125 is a member capable of providing heat transfer to the second pipe 123, and may be processed in various forms. That is, it can be installed in a form provided in the second tube 123 as well as the form surrounding the fraudulent second tube (123). Therefore, by providing the heat transfer around the second tube 123 using the temperature adjusting unit 125 changes, that is, increases the ambient temperature of the second tube 123. Then, the pressure of the second tube 123 is higher than the pressure of the first tube 121. Therefore, due to the pressure difference between the second tube 123 and the first tube 121, the medicine sucked into the first tube 121 may be dropped into the cell 10.

In addition, the pump 127 may be used to suck the medicine, that is, the reagent or the sample at a very slow speed even without maintaining the correct flow rate without using the temperature adjusting unit 125 or the capillary phenomenon. In the case of using the pump 127, when the chemical is injected into the first tube 121 by the pump 127, the free fall due to the gravity weight of the drop formed at the end of the first tube 121 is Occurs. In addition, the medicine may fall into the cell 10 due to the free fall. Therefore, the dropping part 12 may include a pump 127, and may connect the pump 127 with the first pipe 121 to suck the medicine through the pumping of the pump 127. In addition, the medicine sucked into the first pipe 121 may be dropped into the cell 10 through the pumping of the pump 127. Here, it is preferable that the temperature adjusting part 125 and the pump 127 are installed as an optional specification as needed.

The device 1 comprises a conveying part 14 for the proper operation of the loading part 12. The transfer part 14 is connected to the dripping portion 12 and has a function of transferring the dripping portion 12 to the upper portion of the cell 10. At this time, the transfer unit 14 is preferably a robot arm for repeatedly transferring the set path. In addition, the robot arm is not required in the injection method of the medicine using the free fall using the pump 127.

The apparatus 1 comprises a detector 16 for measuring the intensity of light emitted by the reaction of the drug, ie, reagent and sample, to find the concentration of metal ions. Since the light is emitted through the window 101 of the cell 10, the light is preferably installed at the bottom surface of the cell 10, that is, directly below the window 101. The detector 16 includes a condenser 161 for condensing the light, an amplifier 163 for amplifying the condensed light, and a current converter 165 for converting the amplified light into a current. Include. Accordingly, the light intensity is measured by condensing the emitted light through the condenser 161, amplifying it through the amplifier 163, and converting the light into a current through the current changer 165. The concentration of the sample material is obtained as the light intensity.

In addition, the apparatus 1 includes a discharge part 103 for discharging the finished drug in the cell 10. Accordingly, the drug that the reaction is completed can be discharged to the outside of the cell 10 through the discharge unit 103. Therefore, when the concentration of the sample material is continuously obtained, the chemicals having completed the reaction are continuously discharged through the discharge part 103.

In addition, the apparatus 1 includes a display unit 18 for displaying the concentration of the sample material obtained by using the detector 16. Therefore, the concentration of the sample material may be confirmed in real time through the display unit 18.

In the device 1 having the above configuration, the cell 10 and the detector 16 are preferably installed in the shielding part 20 which is isolated from the outside. This is because the reaction to emit light in the cell 10 takes place, and the detector 16 measures the emitted light, so as to block the outside to improve the efficiency of the measurement. In addition to the cell 10 and the detector 16, the entire device 1 may be installed where it is isolated from outside.

Looking at the method for obtaining the concentration of the sample material using the analysis device as follows.

2 is a flowchart illustrating a method of analyzing a sample material according to an embodiment of the present invention.

Referring to Figure 2, a reagent and a sample are prepared. (S20) The reagent is a chemical that produces a chemiluminescence phenomenon. Specifically, the reagent includes luminol and hydrogen peroxide. In addition, the sample may include a sample material such as a metal ionic material, a bio material, an environmentally harmful substance, or another compound. Fe, Cu, Cr, Co etc. are mentioned as an example of the metal ion substance for calculating | requiring the density | concentration by the said analysis method. And as an example of the said biomaterial, adrenaline is mentioned. The sample is a solvent of the sample material, water, ammonia water, inorganic acids such as hydrofluoric acid, hydrochloric acid, sulfuric acid and the like, C ₁ -C ₆ water-soluble saturated alcohol (C ₁ -C ₆ is 1 -A 6 -membered carbon compound). These can be used individually or in mixture. Thus, the sample comprises the sample material and the solvent.

Then, the reagent is provided in the cell. (S22) Specifically, the reagent is sucked into the dropping portion using the dropping portion. At this time, the reagent is preferably aspirated by the capillary phenomenon using a capillary tube. In addition, it may be sucked by forced suction using a pump connected to the dripping portion. Then, the dropping part is transferred to the upper part of the cell using the transfer part, and then the aspirated reagent is dropped into the cell by free fall, pressure change due to a temperature difference using the temperature adjusting part, forced discharge using the pump, and the like. . Subsequently, the sample is sucked into the dropping tube. (S24) The suction of the sample is the same as that of the reagent. The dripping portion is transferred to the upper portion of the cell by the transfer portion.

Subsequently, the aspirated sample is dropped into the cell (S26). That is, the sample is dropped onto the surface of the reagent. Here, it is preferable that the said sample falls intermittently. In addition, the sample falling intermittently is preferably about 1 to 100 μl drop each time, and more preferably about 20 to 50 μl drop. Here, the amount of the falling sample is not limited and depends on the properties of the capillary and the pump to be put, so that the measurement can be measured even if the amount is reduced or increased. And dropping the sample is also achieved by the same method as dropping the reagent. Accordingly, the sample diffuses along the surface of the reagent in the cell, as shown in FIG. 3 (S28) The surface of the reagent (sample direction) causes the reagent and the sample to react for a sufficient time. . Then, the reagent and the sample that reacted for the sufficient time are discharged. (S30)

Light is emitted by the reaction due to the surface diffusion (S32). The emitted light may be converted into a current through condensing and amplifying. In this way, the intensity of the light is measured by converting the light signal into an electric current (S34). The concentration value of the sample material contained in the sample can be obtained by treating the light intensity with an electric current (S36). In addition, the concentration value of the sample is displayed through a device such as a monitor so that the observer can recognize it (S38).

In fact, in order to obtain the concentration of the sample material, the light intensity is obtained by changing only the concentration of the sample material while maintaining all the conditions such as the solvent, the pH of the solution, the concentration of the luminol and the falling amount of the sample. A standard calibration curve is obtained showing the intensity of the light according to the concentration of the sample material. Then, the light intensity of the sample including the sample material to be obtained is measured, and through this, the concentration of the sample material included in the sample is obtained from the obtained standard calibration curve.

By applying the method and apparatus of the present invention to determine the concentration of the sample material, it is possible to maximize the consumption of the drug including the reagent and the sample, to accurately perform the analysis of ppb to ppt unit, and to minimize the analysis time. This is because the reaction for the analysis consists of surface diffusion. In addition, since the device of the present invention has a simple configuration, the cost for making the device is reduced, and space constraints are reduced.

Hereinafter, the characteristic with respect to the dripping part of this invention is demonstrated.

Figure 4 shows the result of measuring the mass of the sample dropped intermittently when using the temperature control unit of the present invention.

Referring to FIG. 4, the sample used for the mass measurement includes about 0.01 molar luminol and at least 18 megohm distilled deionized water. In some cases, IPA may be used instead of the water. And, the first tube of the dripping portion varies depending on the sample put in the diameter, but about 0.1-1.0 mm is used.

As a result of the measurement, when the sample was set to about 0.02g each time, it was confirmed that the sample falls very uniformly. That is, it could be confirmed that about 20 μl of sample dropped intermittently at regular intervals. Therefore, in the present invention, when the sample is sucked into the dropping portion by capillary action and then the dropped sample is dropped using the temperature adjusting portion of the dropping portion, a certain amount can be dropped intermittently.

5 shows the result of measuring the mass of the sample dropped by the free fall according to the present invention.

Referring to Figure 5, the sample is the same as the sample used in the measurement of Figure 4 but using a pump, the volume of the sample for free fall is achieved by adjusting the size of the capillary tube.

As a result of the measurement, the sample was confirmed that approximately 0.01g falls constantly every time. That is, it was confirmed that about 10 μl of sample dropped intermittently at regular intervals. Therefore, in the present invention, if the sample is sucked into the dropping portion by capillary action and then the sample is dropped by free fall, a certain amount can be dropped intermittently.

As such, when using the dropping portion of the present invention, a sample having a certain amount can be dropped intermittently. And a capillary phenomenon can be obtained by using the dripping part which has a 1st tube about 0.1-1.0 mm in diameter, and a sample can be dropped in small quantities about 1-100 microliters. Therefore, when the concentration of the sample material is obtained using the method and apparatus of the present invention, not only excellent reproducibility can be secured but also the consumption of the sample can be minimized.

Hereinafter, the characteristics of the cell of the present invention will be described.

6 shows the light transmittance according to the material of the window of the cell of the present invention.

Referring to FIG. 6, a sample including the reagent and 5 ppb Fe was prepared in the above to measure the transmittance. The transmittance of light emitted by the surface diffusion reaction in the cell was measured.

As a result of the measurement, when the window has a PDMS (DAPI-P cell) material as in the first example it can be seen that the transmittance of about 3,000 in the wavelength range of 500 to 1,500nm. This is similar to the transmittance in air as in the second example. And, as in the third and fourth examples, when the window has a glass material, it can be seen that the transmittance is about 2,700 in the wavelength range of 500 to 1,500 nm.

Therefore, since the PDMS material, which is a window of the cell of the present invention, is resistant to various acids, it is possible to secure reliability in measuring the concentration of metal ionic substances dissolved in such acids. Similar results can be obtained for PMMA, an optical polymer. In particular, in the present invention using only a small amount of the sample, it is possible to more actively secure the reliability of the measurement through securing the transmittance.

Hereinafter, a method for obtaining a standard calibration curve representing concentrations of Fe (II), Cu (II), Cr (III), and Co (II) in the sample material under given conditions, and for each Fe (II) and Cu ( II), a test example for obtaining the concentrations of Cr (III) and Co (II) will be described.

In an apparatus for implementing the method, the position of the detector is important. In other words, it is necessary to increase the sensitivity by collecting more light emitted by the reaction of the drug. Therefore, the detector is preferably installed at the bottom of the cell. The amplifier uses a photomultiplier (PMT), and the current converter uses a picoammeter of Keithley company (486 autoranging). And, the water used as the solvent of the sample is 18MΩ distilled water prepared by the deionization system of Barnstead company (Barnstead company), the luminol contained in the reagent was prepared by Sigma-aldrich company (Sigma-aldrich company) use.

Standard calibration curve of Fe (II) and test example 1

A standard Fe (II) solution is prepared to obtain a standard calibration curve of Fe (II). Specifically, luminol is prepared from sodium thereof as a reagent and recrystallized from an aqueous alkali solution to be purified. The H ₃ BO ₃ concentration is kept constant, and the amount of KOH is changed to prepare a 0.1 M KOH-H ₃ BO ₃ buffer solution having a pH of 11. Next, purified luminol sodium is dissolved in KOH-H ₃ BO ₃ buffer solution and adjusted to 0.01M. In addition, a 10,000 ppm solution of a standard solution prepared by the US National Standards Institute (NIST) is purchased as a sample, and a part of the standard solution is diluted to prepare a 2.0 ppb standard Fe (II) solution. Subsequently, follow the same procedure as above, but partially dilute the stock solution to prepare 5 ppb, 10 ppb and 20 ppb of standard Fe (II) solution.

Accordingly, the intensity of light for each of the above standard Fe (II) solutions was measured using the apparatus of the present invention. As a result of the measurement, as shown in FIG. 7, a standard calibration curve of Fe (II) having a straightness of 0.9908035 was obtained.

The concentration of metal ions was determined four times for a 10 ppb standard Fe (II) solution sample by the apparatus and method of the present invention. As a result of the measurement, as shown in Figure 8, it was confirmed that the peak is formed at 2.0V. Thus, it can be seen that the measurement has excellent reproducibility by showing a similar pattern four times.

Standard calibration curve of Cu (II) and Test Example 2

A standard Cu (II) solution is prepared to obtain a standard calibration curve of Cu (II). Reagents and samples are the same as for Fe (II). NIST solution is purchased and used as a sample. Some of the solution is diluted to prepare 5 ppb and 10 ppb of standard Cu (II) solution.

Accordingly, the intensity of light for each of the above standard Cu (II) solutions was measured using the apparatus of the present invention. As a result of the measurement, as shown in FIG. 9, a standard calibration curve of Cu (II) having a straightness of 0.99887 was obtained.

And the concentration of metal ion was calculated | required three times about the sample of 0.15 ppb standard Cu (II) solution by the apparatus and method of this invention. As a result of the measurement, as shown in Figure 10, it was confirmed that the peak is formed at 0.15V. Thus, by showing similar patterns throughout the three it can be seen that the measurement has excellent reproducibility.

Standard calibration curve of Cr (III) and test example 3

A standard Cr (III) solution is prepared to obtain a standard calibration curve of Cr (III). A portion of the stock solution purchased from NIST is diluted to prepare 50 ppt of standard Cr (III) solution. Subsequently, follow the same procedure as above, but dilute a portion of the stock solution to prepare 100ppt, 300ppt and 500ppt of standard Cr (III) solution.

Accordingly, the light intensity for each of the above standard Cr (III) solutions was measured using the apparatus of the present invention. As a result of the measurement, as shown in FIG. 11, a standard calibration curve of Cr (III) having a straightness of 0.99273 was obtained.

The concentration of metal ions was determined four times for a 500 ppt standard Cr (III) solution sample by the apparatus and method of the present invention. As a result of the measurement, as shown in Figure 12, it was confirmed that the peak is formed at about 1.0V. Thus, it can be seen that the measurement has excellent reproducibility by showing a similar pattern four times.

Hereinafter, a method for obtaining a standard calibration curve showing the concentrations of Fe and Cu including DHF (Dilute HF) under given conditions and a test example for obtaining respective metal ion concentrations thereof will be described.

In an apparatus for implementing the method, the amplifier uses a photomultiplier (PMT) and the current converter uses a picoammeter of Keithley company (486 autoranging). And, the water used as the solvent of the sample is 18MΩ distilled water prepared by the deionization system of Barnstead company (Barnstead company), the luminol contained in the reagent was prepared by Sigma-aldrich company (Sigma-aldrich company) use. And the window of a cell constitutes what has PDMS material. In addition, the DHF is a solution mainly used in the cleaning process to effectively remove metal contaminants contained in the oxide.

Standard calibration curve of Fe containing DHF and test example 4

A standard Fe solution containing DHF is prepared to obtain a standard calibration curve of Fe containing DHF. Then, a portion of the NIST stock solution was diluted to prepare a 5 ppb standard Fe solution containing DHF. Subsequently, follow the same procedure as above, but partially dilute the stock solution to prepare 10 ppb and 20 ppb standard Fe solutions.

Accordingly, the intensity of light for each of the standard Fe solutions containing the DHF was measured using the apparatus of the present invention. As a result of the measurement, as shown in FIG. 13, a Fe standard calibration curve including DHF having a straightness of 0.99951 was obtained.

The concentration of metal ions was determined four times for the 5 ppb Fe sample by the apparatus and method of the present invention. As a result of the measurement, it was confirmed that the peak is formed at 0.5V, as shown in FIG. Thus, it can be seen that the measurement has excellent reproducibility by showing a similar pattern four times.

Standard calibration curve and fifth test example of Cu containing DHF

To obtain a standard calibration curve for Cu containing DHF, a standard Cu solution containing DHF is prepared and tested as in the case of Fe. A portion of the stock solution is diluted to prepare 10 ppb and 20 ppb of standard Cu solution.

Accordingly, the intensity of light for each of the standard Cu solutions containing the DHF was measured using the apparatus of the present invention. As a result of the measurement, as shown in FIG. 15, a Cu standard calibration curve including DHF having a straightness of 0.98719 was obtained.

And the concentration of metal ion was calculated | required three times with respect to a 5 ppb standard Cu solution sample by the apparatus and method of this invention. As a result of the measurement, as shown in Figure 16, it was confirmed that the peak is formed at 1.2V. Thus, it can be seen that the measurement has excellent reproducibility by showing a similar pattern three times. In particular, the experimental results showed similar results with DHF in hydrochloric acid, nitric acid, sulfuric acid, etc., diluted from 5: 1 to 100: 1 by volume of concentrated acid.

Test Example 6

In the sixth test example, the concentration of the bio-material containing adrenaline was measured. Specifically, 0.1 M of luminol in aqueous solution was adjusted to pH 13 with 0.5 M NaOH, and then 0.01 M of periodic acid was prepared, and the adrenaline concentration was 10 ^-4 M, which was measured by the above apparatus and method.

As a result of the measurement, as shown in FIG. 17, it can be seen that 10 ⁻⁴ mol of adrenaline shows a signal strength of 1 volt or more. Thus, when using the apparatus and method of this invention, the density | concentration of a biomaterial can also be measured easily.

As described above, the method and apparatus of the present invention not only inspect the water quality of a manufacturing line of a semiconductor device, a general water and sewage system, a nuclear power plant, a water tank of a public house, an inspection of suspended matter in the air, but also an automatic detection of a biomaterial, Because of its availability, its application is very wide.

According to the present invention, the intensity of light is measured through a reaction by surface diffusion, and the concentration of a sample such as a metal ion, a biomaterial, an environmental sample, or another compound is determined based on the light intensity. Thus, by securing the reaction area wider by using the reaction by the surface diffusion, in the case of metal ions, it is possible to accurately analyze the ppb to ppt unit. In addition, even when a small amount of the sample is used, the concentration of the sample can be obtained, thereby reducing the amount of sample consumed when the concentration of the sample is obtained. In addition, the analysis time is reduced. Moreover, the range of application is also effective. In addition, the conventional apparatuses have problems such as reproducibility, continuity, contamination control, maintenance of the device, etc. caused by the use of a peristaltic pump syringe pump to inject a sample, but in the case of the present invention can solve the above problems.

Therefore, the use of the method and apparatus can be expected to contribute to industrial development.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. I can understand that you can.

Claims (19)

a) preparing a reagent in a cell in which chemiluminescence occurs; b) preparing a sample in a tube containing a sample material to be analyzed; c) dropping the sample provided in the tube into a reagent in the cell to diffuse the sample onto the surface of the reagent; And d) determining the concentration of the sample material by measuring the intensity of light emitted through the reaction by the surface diffusion. The method of claim 1, wherein the reagent comprises luminol and further comprises hydrogen peroxide, periodate, or a mixture thereof. The method of claim 1, wherein the sample material is at least one selected from the group consisting of metal ionic materials, biomaterials, environmentally harmful substances and other compounds, and the metal ionic materials consist of Fe, Cu, Cr and Co. At least one selected from the group consisting of. The method of claim 1, wherein the sample is a water-soluble saturated alcohol of water, ammonia water, mineral acid, C ₁ -C ₆ (C ₁ -C ₆ represents a carbon compound having 1-6 carbon atoms) or a mixture thereof Further comprising a solvent, wherein the inorganic acid is at least any one selected from the group consisting of hydrofluoric acid, hydrochloric acid, nitric acid and sulfuric acid. The method of claim 1, wherein the sample is provided in the tube by suction indicated by a capillary phenomenon or in the tube by forced suction of a pump. The method of claim 1, wherein the sample falls intermittently into the cell by free fall, or intermittently falls into the cell as a pressure change due to a temperature difference in the tube exhibited by electric heat. Characterized in that it intermittently falls into the cell by discharge. The method of claim 6, wherein the intermittently falling sample is dropped by 1 to 100 μl each time. The method of claim 1, wherein a) -d) is repeated at least once. The method of claim 1, wherein a) comprises: preparing the reagent in a tube; And Dropping the reagent in the tube into the cell. A cell having a window capable of surface diffusion of the drug and having a window transmitting light emitted by the reaction of the drug; A dropping portion having a first tube for sucking the medicine and dropping the medicine sucked in the first tube into the cell; And Located in the bottom portion of the cell, the analyzer of the sample material including a detector for obtaining the concentration of the sample material to be analyzed by measuring the intensity of the emitted light in real time. The method of claim 10, wherein the drug comprises a reagent in which chemiluminescence occurs and a sample material to be analyzed, wherein the sample material is selected from the group consisting of metal ionic materials, biomaterials, environmentally harmful substances and other compounds. At least one of the analysis apparatus for a sample material, characterized in that. The apparatus of claim 10, wherein each of the cells and windows is made of optical glass, quartz, or optical polymer, and the optical polymer is PDMS or PMMA. The sample material according to claim 10, wherein the cell is of a cylinder type having a base of 8-12 mm in diameter or a cube type having a height of 3-15 mm and having a volume similar to that of the cylinder type. Analysis device. The apparatus of claim 10, wherein the first tube is a capillary tube capable of inhaling the drug by capillary action. 11. The apparatus of claim 10, wherein the dripping portion further comprises a second pipe connected to the first pipe and a temperature adjusting part for adjusting an ambient temperature of the second pipe, and the first pipe being adjusted by the temperature adjusting part; An apparatus for analyzing sample material, characterized in that the drug is dropped by a sufficient pressure change due to the temperature difference of the second tube. The sample of claim 15, wherein the temperature controller includes a coil and a power applying unit configured to apply power to the coil, wherein the coil surrounds the second tube or is provided inside the second tube. Analytical device of matter. The apparatus of claim 10, wherein the dripping unit further comprises a pump connected to the first tube. The method of claim 10, wherein the detector, A light collecting unit attached to a bottom surface of the cell and configured to collect light transmitted from the window of the cell; An amplifier for amplifying the focused light; And And a current changer configured to convert the amplified light into a current. The apparatus of claim 10, wherein the cell and the detector are installed in a shielding part which is isolated from the outside.