TW528867B - Electrochemical assay using an electroconductive diamond-coated electrode, and electrochemical assay system based thereon - Google Patents

Abstract

This invention provides, in its first aspect, electrochemical assay using a conductive diamond-coated electrode suitable for quantification of solid metals. The method consists of using a boron-doped diamond coated electrode (conductive diamond electrode), rubbing the conductive diamond electrode against a test object, to allow thereby part of the object to be transferred by friction to the surface of the conductive electrode, immersing the conductive electrode carrying the metal in an electrolyte solution, shifting stepwise the potential of the conductive electrode from a negative level towards the positive side, thereby dissolving the object adhered to the electrode into the electrolyte solution, and detecting the current change in response to the stepwise shift of potential, for analysis of the test object. The invention, in its second aspect, provides electrochemical assay using a conductive diamond electrode suitable for quantification of ionizing metals. The method consists of depositing a test object dissolved in a solution on the surface of the diamond electrode by sweeping the potential of the electrode towards negativity, then sweeping the potential of the electrode towards the positive side, thereby dissolving the metal deposited thereon to the solution, and detecting the current change in response to the potential step, for analysis of the test object. The invention, in its third aspect, provides a flow-cell based electrochemical assay system using a conductive diamond electrode or an anodically oxidized diamond electrode suitable for quantification of organic materials whereby plural test materials are stably assayed sequentially. The method consists of using, as an active electrode, a conductive diamond electrode, or an anodically oxidized conductive diamond electrode. The system includes a flow-cell incorporating the active electrode together with reference and opposite electrodes, and an electrochemical assay unit connected to the flow-cell. With this system, assay consists of introducing a sample solution containing a test object into the flow-cell, applying a voltage between the active electrode and opposite electrode for electrochemical analysis, disposing of the solution after analysis, and repeating the same process for another test object, until the whole series of samples are completely analyzed. The invention, in its fourth aspect, provides uric acid assay using an anodically oxidized diamond-coated electrode suitable for selective quantification of uric acid independently of ascorbic acid which may be coexistent in a same biological sample. The anodically oxidized diamond electrode makes it possible to clearly separate the potentials at which current peaks ascribable to uric acid and ascorbic acid occur in a current characteristics chart used for assay. The assay is also applicable to a flow-cell based assay system for sequential analysis.

Description

528867 A7 _B7_ V. Description of the invention (1) Background of the invention (please read the precautions on the back before filling this page) First, the present invention relates to an electrochemical analysis method using conductive diamond-coated electrodes suitable for quantifying solid metals, in which testing Metal is transferred to the electrode by friction; second, the present invention relates to the same analytical method suitable for quantifying ionized metals, wherein the test metal is transferred to the electrode by electroplating; third, the present invention relates to coating with conductive diamond suitable for quantifying organic sample solutions Flow injection electrochemical analysis system for electrodes or anode vaporized diamond-coated electrodes. Fourth, the present invention relates to uric acid analysis suitable for selective quantification of uric acid from ascorbic acid alone (usually coexisting in the same biological test material). Method, and a uric acid analysis system based on it. Prior art Recently, diamond has been known to have excellent electrochemical properties (especially in terms of stability), so diamond is expected to replace the conventional sulphur electrode in electrochemical analysis. Diamond itself has a high resistance, so it is an excellent insulator. However, if boron is doped as an impurity, the resistance of diamond decreases. Therefore, by adjusting the amount of boron added to the diamond, the resistance of the diamond can be placed at any desired position between the highly conductive metal and the semiconductor resistance. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the conductive diamond electrode has many other advantages: compared with conventional electrodes, it has a wider potential range and can generate low background current when used as an electrode. Therefore, the prospect of introducing diamond electrodes into chemical analysis has attracted widespread attention. Indeed, a conductive diamond electrode can detect electrochemical oxidation at high potentials because it has a wide range of potentials. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 _B7_ V. Description of invention (2) Electrochemical analysis is widely used in various fields, including metal industry, environmental science, energy chemistry, imaging engineering , Electronics, biology, medicine, etc. (Please read the notes on the back before filling out this page.) For this type of electrochemical analysis, a system as described in Figure 1 is routinely used. This system can be used, for example, to analyze test objects (eg, metals) in a solution. In this figure, 1 indicates a container for analysis. It contains the electrode metal 1a, which contains the test object (for example, metal ions) to be analyzed. This container is sealed with a sealing film 1b. The active electrode 2 and the counter electrode 3 are placed so that they are immersed in the electrolytic solution 1a in the analysis container 1 at a specific distance from each other. The active electrode 2 is composed of, for example, a graphite electrode, a glass sulphur electrode, a mercury electrode (for example, a mercury-coated electrode or a mercury drop electrode), or the like. The counter electrode 3 is composed of, for example, a lead or sulfon electrode. The active electrode 2 and the counter electrode 3 are connected to the potentiostat 4 through wires 2a and 3a, respectively. A potentiometer 4a and a recorder 4b are connected to the upper ring of the potentiostat 4. The reference electrode 5 (or the base electrode) is electrically connected to the active electrode 2 through a capillary 5a, and is electrically connected to the potentiostat 4 through a lead 5b. The reference electrode 5 is composed of a saturated calomel electrode. The feeding tube 6 supplies nitrogen (N 2) near the counter electrode 3. The stirrer 7 rotates the disk 7a on the bottom of the analysis container 1, so that the electrolyte 1a can be stirred in the analysis container 1. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the following method of analyzing metals in the first drawing. First, the potentiostat 4 scans the potential of the active electrode 2 from the original level to a negative value, so that the electrolyte can be electroplated. The metal ions are continuously deposited on the surface of the active electrode 2 (reduction and concentration). Then, the potentiostat 4 scans the potential of the active electrode 2 to a positive value. -4- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 ---- B7___________ 5. Description of the invention (3) (Please read the precautions on the back before filling this page) ® The metal deposited on the active electrode can be dissolved in the electrolyte la by anode peeling. Each deposited metal dissolves at a characteristic oxidation potential. Therefore, if the metal is dissolved in the electrolytic solution la, the metal can be analyzed by detecting the current change in response to the potential change of the active electrode 2 at the required scanning speed. The system as depicted in Figure 1 does perform electrochemical analysis of metal ions in the electrolyte. However, if the test substance is solid, it must be dissolved in the electrolyte before it can be deposited on the active electrode for analysis. This is time consuming and may damage the test substance during processing. Therefore, this system applies only to a limited range of substances. Even if the test object is a metal ion, the conventional system as shown in Fig. 1 has another problem. Take, for example, conventional electrochemical analysis using a mercury drop electrode or a mercury-coated electrode (hereinafter referred to as a mercury electrode). The method includes: reducing metal ions in the metal on the surface of the mercury electrode, so that the metal can be assimilated to or amalgamated to the surface of the mercury electrode, and the potential of the amalgam electrode can be scanned, so that The electrode was subjected to anodic peeling; then a current in response to a change in potential was measured. The conventional rules printed by sulphur electrodes or mercury electrodes of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs can be used for analysis including 1.0X ΙΟ " 6 M Pb (NO) 3 Ν 1. ΟΧ ΙΟ * 6 M ZnS04. 1. 〇Χ ΙΟ * 6 Μ

Electrolytic solution of Cu (N03) 2, 〇μικCl and Η2〇 (pH value 3.3). The analysis process includes: maintaining the potential of the active electrode at -1200iaV for 90 seconds, which can deposit metal ions on the active electrode, scan the potential of the active electrode to a positive value, and then measure the scan rate at 50 in V / s Current change in response to potential change at lower voltage ^ -5- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 ___ B7___ V. Description of the invention (4) The result is shown by the far line in Figure 2 g (analysis based on sulphur electrode) and 11 (analysis based on mercury electrode) are given. As shown by these far lines, the change in current in response to a change in potential when the deposited metal is dissolved in the electrolyte is recorded. Zn, Pb, and Cu can be analyzed by reading the potential at which a peak current (in this case, a minimum value) is generated. However, if a sulfonic electrode is used in the system, those peaks attributable to Cu and Zn ions become unclear. On the other hand, if a mercury electrode is used, the observed peak potential due to Hg ions is higher than the potential due to the peak current generated by Cu ions. The reason that Hg ions that are not intentionally added to the solution can be detected can be explained as coating The electrode-coated Hg was dissolved in the solution. Therefore, it is impossible for this system based on a mercury electrode to detect metal ions such as Pt having a vaporization potential higher than Hg ions. In addition, this conventional system, as depicted in Figure 1, is unlikely to completely oxidize the deposited metals because these metals can continue to exist as impurities in the electrodes through amalgamation. This will gradually reduce the reliability of the mercury electrode after each analysis. Therefore, if the same mercury electrode is used repeatedly for analysis, then these ----: 1 ---- ΜΨ -------- order , -------- Line · (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In order to analyze and dye in the local environment between C, it is necessary to separate the pollution. The C pole places a new idea in the power management system, which is subject to change and changes from time to time. You must ask this question about the problem of extracorporeal mercury. The product liquid belonging to B Jinsheng will dissolve the material and test the mercury. The waste material from the electricity will be removed by electricity. There is heavy solution in the solution. This is not as good as its living thing. The biomass holding device is in the group with amine. The sample sample is produced in the set containing the test package in the amine pair. Ε 3 centimeters, 1 male, 297 X ο 21 / — \ standard gauge Α4 S) Ν (C Appropriate rule paper for the standard country and country i Paper 528867 A7 —_____ B7 V. Description of the invention (5) (Please read the precautions on the back first (Fill on this page) A missing amine. In fact, a small amount of histamine is found in a variety of plants and fruits, so it will not be harmful as long as it is present. But if fermented food and condiments such as beer, oil-preserved fish , Wine, etc. are not processed in a sufficient manner, their histamines contain The amount will increase, so people who accidentally consume this food will produce diseases of the digestive tract, cardiovascular system or nervous system. Histamine is a chemical medium that causes different reactions to obesity and various related vasoconstriction. Therefore, Histamine is very important in test samples. For the determination of histamine, electrochemical analysis systems with flow cells have been widely used because this allows continuous analysis when combined with liquid chromatography. The analysis package performed by the electrochemical analysis system: each sample solution containing the test object dissolved in the buffer is guided to the flow cell through mercury, and a voltage is applied between the active electrode and the counter electrode in the flow cell, so that The reaction between the active electrode and the counter electrode is caused to generate a signal, which is then transmitted to an analysis device including a potentiostat and an analyzer (personal computer or similar device), so that the signal is controlled and analyzed. The buffer in the system is a solution added to the test substance to facilitate the electrochemical determination, or for example A solution that controls the pH of the sample solution. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in this electrochemical measurement system, a glass sulfonate electrode is usually used as the active electrode held in the flow cell. Why use a glass sulfonate electrode as an activity The electrode can be interpreted as: glass sulphur, such as pyrolytic graphite, has very high conductivity, is stable to chemical action, and does not permeate gas. In addition, it is cheaper and has better performance in the presence of hydrogen or oxygen. A paper size applies Chinese national standards. (CNS) A4 specification (210 X 297 mm) 528867 A7 _ ^ _ B7_ V. Description of the invention (6) High overpotential. (Please read the precautions on the back before filling this page) But when measuring histamine, use The conventional system of glass sulphur electrodes is difficult because histamine undergoes electrochemical oxidation at high potentials. In addition, if the same phosphate buffer is repeatedly used for a long time, the accuracy of the measurement will gradually decrease, so it is impossible to obtain accurate results repeatedly with the same electrode for a long time. Section 3 shows the measurement results of 50 # Μ dehydronicotinamide adenine dinucleotide (NADH) obtained in the electrochemical measurement system in a 0.1M buffer (pH = 7). Glass master electrodes are used as active electrodes. As shown in the figure, the characteristic graph obtained at the initial measurement stage with a new glass sulphur electrode is very different from the characteristic graph obtained after 1 hour of measurement with the same electrode. This problem is particularly acute if uric acid is to be distinguished from ascorbic acid, which usually coexists in the same biological sample. Uric acid is an end product of the metabolism of purine in the body: it is derived from the purine contained in the muscle extrinsically, and is essentially a degradation product of tissue nucleic acid, or a direct product synthesized without nucleic acid. In serum, some uric acid binds to serum proteins, and the rest is free. It is printed in the red blood cell by the Intellectual Property Bureau of the Intellectual Property Bureau of the Consumer Consumption Cooperative, and Xie bleeds in the 1-diacid acid, which is a new example of urination of the urine tube. The number of human bodies has been passed into the urine. The number of major polyuric acid in the urinary urinary urinary urinary system is shown in the figure. However, in the C section, the urinary purine is measured in the middle tube and the blood is filtered. Divided into 8 kidneys. The blood in the department is 0. Overcharged. There are several 4-pass blood-sucking, only 0. Can be controlled acidity is large acidic urinary thick, acidic urine high kidney quilt. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 Α7 Β7 V. Description of the invention (7) (Please read the precautions on the back before filling this page) In case of gout), Acid is secreted from the abnormal increase in kidney ridges. But hyperuricemia also occurs during hypertension and obesity. Therefore, hyperuricemia has attracted attention as a disease response of abnormal metabolism. To determine uric acid, reduction methods and urase (enzyme) methods have been used. (a) Reduction method The reduction method is based on a reaction in which uric acid is reduced to a compound capable of producing tungsten blue when it is brought into contact with a dish salt in an alkaline solution. Various alkalizing agents have been developed to increase the sensitivity of the reaction, to prevent turbidity of the anti-88 solution, or to stabilize the color. Among them, the Caraway method using sodium and its variants are widely used. Anti-substances other than uric acid in serum include ascorbic acid, stilbene compounds, and phenol. The effect of ascorbic acid is substantially eliminated by adding Alkaline® 'to the sample or to a protein-loss sample and then leaving the resulting sample. The following describes the phosphotungstic acid_gastric method. First, its principle is introduced. Sodium sulfonate was added to the serum filtrate due to the addition of tungstate _ @ less protein to break down the chromogen that is not related to uric acid. Then, the phosphorite salt reagent was added, and the developed tungsten blue was color-coded. Urea was also added to prevent the reaction solution from being cloudy. The reagents used by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperatives include protein-removing tungstates, original phosphotungstate solutions, phosphotungstate solutions appropriately adjusted according to use, 14% sodium sulfonate-urea solution, and uric acid A standard solution of uric acid at a concentration of 100 mg / dl. To obtain a standard curve, a 1000 mg / dL uric acid standard solution was serially diluted with water before the measurement. The concentration of the diluted solution corresponds to the concentration of uric acid in the serum. If the standard curve is linear, then the standard curve for a given test can only be determined by measuring water (blank) and 0.5 mg / min. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7_ V. Description of the invention (8) It is obtained by increasing the reaction strength of uric acid standard solution. (Please read the precautions on the back before filling this page) The test is performed as follows: First, add 1.0 ml of serum, 80 ml and 0.5 ml of 2 / 3N sulfuric acid to the flask and mix, and add 0.5 ml to it. 10% sodium tungstate, then they were stirred and mixed and left for 20 minutes. The contents were transferred to a medium-sized test tube and then centrifuged for 10 minutes at 3 000 r p in. Then, take three medium test tubes A, S and B: Tube A receives 3.0 ml of supernatant; tube S is 3.0 ml of standard solution, and tube B is 3.0 ml of water (blank). 1 ml of sodium sulfonate and 1 ml of urea solution were added to each test tube for mixing, and then the mixture was left for 2 Q minutes. 0.5 ml of approximately adjusted phosphotungstate solution was added to each test tube for thorough mixing, and then the mixture was left for 15 minutes for complete color development. Within 30 minutes thereafter, test tubes A and S for light absorption at 710 nm (or 660 nm may be used), and use the absorption value of tube B as a comparison. The relative absorption measurements are expressed as E a and Es, then the serum concentration of uric acid can be obtained from the following equation: Serum concentration of uric acid = (EA / ES) X 5 mg / L (b) Uricase method Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Printed uric acid is an enzyme that oxidizes uric acid to allantoin and hydrazone 202, which has a high degree of uric acid to be anisotropic, so it is widely used to determine the uric acid content in biological samples. This method includes various types: 0)-One method is to use the principle that uric acid has the maximum absorption at 2 3 3 nm. Before and after reacting the sample with urase, determine the light absorption of the sample at 2 3 3 nm, and then pass Determination of anti--10- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7_ V. Description of the invention (9) (Please read the precautions on the back before filling this page) Decrease in light absorption to determine the uric acid content in the sample; ⑵ Another method is to covalently link urase to peroxidase, which can produce H2 02 in the presence of uric acid and then oxidize 4-aminoantipyrine -Phenol strip (or aniline strip) or MBTH-DMA strip to develop color; ⑶ Another method is to covalently link urase and catalase, so that H2 02 can be produced in the presence of uric acid, and then Methanol is oxidized to formaldehyde, which is developed by the acetone-acetone method; and another method is based on an enzyme-immobilized membrane electrode that immobilizes urase on a membrane that selectively penetrates H2 02 and then wraps it with the membrane Η 2 0 2 Pole obtained. The urase-hydroxidase method and the urase-peroxidase method are described below. First, the urase catalase method is given. The principle is described below. According to this method, urase is reacted with uric acid to obtain Η2 02; Η2 02 oxidizes methanol to formaldehyde in the presence of catalase; formaldehyde appears yellow under the action of acetamidine and ammonium salt; then the color Colorimetric at 4 10 nm. This method has excellent heterogeneity and accuracy, and is not affected by the interference of various coexisting substances. However, this method requires a blank sample because it uses a relatively short wavelength beam. There are two ways to prepare a blank sample: one is to remove the protein, and the other is the solvent itself. The latter is generally used. The reagents printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include methanol / acetone solution, pergassed argon / ammonium salt solution, urase / catalase / ammonium salt solution, 1Q0 mg / dL of uric acid raw material solution, 10 mg / dL standard solution of uric acid and so on. Generally, as long as the uric acid content in a given sample is measured, the 1 G 〇mg / dL standard uric acid standard raw material solution is diluted to 2, 4, 6, 8, and 10 milliliters. 1 This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 _B7_ V. Description of the invention (1) g / dL solution; the uric acid content of each solution is measured by the same test method to obtain a standard curve; if this The curve is basically linear, only the current intensity corresponding to the standard solution (containing 10 mg / dL of uric acid) is measured, regardless of whether the uric acid content of the sample used needs to be determined. The test is performed as follows: First, take four test tubes A, B, S and SB: tubes A and B receive 2. G ml samples (if the sample is urine, diluted 10 times with water); then tubes S and SB receive 0 2 ml of a standard solution containing 10 mg / dL of uric acid. Add 1 ml of methanol / acetone precipitation to each test tube for mixing. Then, test tubes A and S for measurement received 2.0 ml of the reaction reagent, and test tubes B and S B used as blanks received 2.0 ml of the blank reagent for mixing. Heat the tube to 37 ° C for 70 minutes. After the reaction was completed, the tubes were cooled with water, and then colorimetrically performed at 710 nm (where water was used as a blank) to determine the light absorption or E a, E s, E b, and E Sfi of the tubes. The serum concentration of uric acid in the test sample can be obtained from the following equation: The serum concentration of uric acid (mg / dL) = 10 × (Ea -Eb) / (Es—ESb) If the sample is urine, the above results must be multiplied by ID Times. (Please read the notes on the back before filling this page) -------- Order- · -------- line. Printed by C. Lin Yinhua, employee of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives After processing. The amine is slightly original, tidinone or its 2 amp test metamisau 20 base color mesogen. Hgbb or Q is first formed into 4-line amine 60. The first will be used to convert benzene to 0-c and then used 5 method oxygen to make枵 Acidification, the absorption of oxygen in the urine of the material is low. It will make the degree of over-coloring 12 and the oxygen will be the most concentrated. _ Over energy can be seeded. The enzyme is a mixture of acid and urine that is produced by the enzyme-producing acid. Urine, D Condensation and narrative method PO agent Xuepi Xing Fang is trying to make the following to make acid according to the cost of urine. According to the standard of the paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 Α7 Β7 5. Description of the invention (11) (Please read the precautions on the back before filling this page) _ pigments in the wavelength range. This increases the sensitivity of the measurement and prevents the hemoglobin and bilirubin contained in the sample from affecting the color development of the pigment. Now a description is given of the addition of N-ethyl N- (3-methylphenyl) -tr-ethanediethylene Method of amine (EMAE) or m-toluidine compound as coupling agent. The reagents used included a 0.1 M phosphate buffer solution (pH 6_0) as a buffer, a coloring reagent containing a 1.2 mM original EMAE solution, and a 10 mg / dl uric acid standard solution. For the measurement, three test tubes A, S and B were taken, and 5 μl of a sample, a standard solution and purified water were added to the tubes A, S and B, respectively. Then, 3.0 ml of the chromogenic reagent was added to each test tube; the mixture was heated to 37 ° C for 5 minutes. Later, the light absorption of the test tubes A and S was measured, and the test tube B was used as a blank to obtain EA and ES. Uric acid concentration is calculated by the following equation: Uric acid concentration = 10 × EA / Es mg / dL But the above routine analysis of uric acid requires skill and time. In recent years, a method has been developed in which one can easily determine the uric acid concentration of a sample on the spot, regardless of whether he is skilled or not. One of the methods includes the use of an enzyme sensor. Recently, diamond-coated electrodes have been developed, and such diamond-coated electrodes have been tested for uric acid analysis. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, it is impossible to directly detect the uric acid in the sample with diamond-coated electrodes. Generally, biological fluids include ascorbic acid and uric acid. For example, the concentrations of uric acid in urine and serum (blood) are about 2 to 2.5 mmol / L and 50 to 60 μL / L, respectively. However, the coexisting concentration of ascorbic acid in the blood is about 20-30 times that of uric acid. Co-existing concentrations of ascorbic acid are the same in urine. In order to adapt to this situation, the sample used for uric acid analysis must be in min. 1 3- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7 V. Description of the invention θ) (please first Read the notes on the back and fill in this page again.) Dilute about 10 0-5 QGG before analysis, because this dilution can reduce the matrix effect of the sample (such as the effect caused by some proteins or other electrochemical chemical biological substances). As uric acid coexists with ascorbic acid as described above, it is difficult for uric acid sensors using diamond-coated electrodes to distinguish uric acid from ascorbic acid because they generate current signals at the same potential. In view of the above problems, the present invention has been made and aims to firstly provide a sensitive, accurate, and rapid electrochemical analysis method that is particularly suitable for quantifying solid metals and that uses conductive diamond-coated electrodes. The method includes: using a polycrystalline conductive diamond electrode doped with a high concentration of boron, rubbing the conductive diamond electrode against a test substance, such as a solid metal such as gold, so that part of the metal is transferred to the surface of the conductive electrode by friction, A metal conductive electrode is immersed in the electrolyte, and the potential of the conductive electrode is gradually changed from a negative value to a positive value by a differential pulse voltmeter method, so that the metal adhered to the electrode is dissolved in the electrolyte, and then the response potential is detected to gradually change The current changes. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Second, the present invention provides an electrochemical analysis method particularly suitable for quantifying ionized metals. The method includes using a conductive diamond-coated electrode doped with a high concentration of boron as an active electrode, immersing the electrode together with a reference electrode in a solution containing an ionized metal such as P b, C d, and then comparing the potential to The reference electrode is scanned to a negative value so that metal is deposited on the surface of the conductive diamond electrode. Then, gradually scan the potential of the conductive diamond electrode to a positive value, so that the metal deposited on it can be dissolved to -1 4-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7 _

1 S V. Description of the invention () (Please read the precautions on the back before filling this page), and then measure the current change in response to the potential step to obtain the current characteristic as a function of the potential. Find the peak on the current characteristic 圔, and then determine the potential at which the peak appears so that the test metal contained in the solution can be analyzed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Third, the present invention provides a flow-injection electrochemical analysis system particularly suitable for quantifying organic substances using conductive diamond-coated electrodes or anodized diamond-coated electrodes. Continuous and stable measurement of multiple test objects. The method includes using a conductive diamond electrode or an anode gas conductive diamond electrode as an active electrode. The anodic oxidation conductive diamond electrode passes a sufficiently strong current by immersing the conductive diamond electrode in an acidic or alkaline solution, causing the diamond electrode to Oxidation reaction, which can apply anode gasification to the diamond electrode. The method is based on a flow cell in which such a conductive diamond electrode or an anodic oxidation diamond electrode is placed, as well as a reference and counter electrode; the electrochemical measurement strip is then connected to the flow cell. Therefore, the method also includes: adding a sample solution containing an organic substance such as histamine to the flow cell, applying a voltage between the active electrode and the counter electrode for electrochemical analysis, processing the solution after analysis, and then repeating the same The process is applied to another test subject until the entire strip is completely analyzed. This flow-cell-based electrochemical analysis system is stable for long periods of time, so it can be used for continuous analysis of samples including various compounds such as histamine with high oxidation potential. Fourth, the present invention provides an electrochemical analysis method using anodized diamond-coated electrodes, which are not suitable for independent and usually coexisting in the same biological sample. -15- This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centi) 528867 A7 B7 V. Description of the invention ί :) and choose to quantify uric acid. The method is based on a uric acid player, in which an anodized conductive diamond electrode, a reference and a counter electrode are placed, and an electrochemical analysis strip is connected to the uric acid sensor. Therefore, the method includes: adding a sample solution containing a test object (eg, uric acid in a biological sample that may also include ascorbic acid) to a sensor, applying a voltage between an active electrode and a counter electrode, and measuring a change in current in response to a potential step, In this way, the current characteristics as a function of potential can be obtained, in which the peak attributed to uric acid is significantly away from the peak attributed to ascorbic acid due to the anodic oxidation of the active electrode, and then the concentration of uric acid in the sample is selected to be determined without interference from ascorbic acid. The method further includes: improving the uric acid sensor into a flow cell, connecting the flow cell to an electrochemical analysis strip placed in a flow cell injection device, and then using the electrochemical flow analysis strip based on the obtained flow cell to analyze multiple samples Continuous selection analysis of uric acid. Brief description of the surrounding house Figure 1 is a schematic diagram of a generally known system for analyzing metals. Fig. 2 shows a graph of the current characteristics as a function of the potential, and shows the results of analyzing the electrolytic solution containing various metal ions using the analysis system as depicted in Fig. 1. Figure 3 shows the current characteristic diagram, which shows the analysis result of 50 # M NADH (in the Q. 1M buffer, the pH value is 7) using the electrochemical analysis system (in which a glass carbon electrode is used). The figure shows the current characteristic diagram as a function of the potential obtained in Example 1, in which the sample S 1 containing lead was analyzed. -16- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ·· ---- ---- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) Figure 5 shows the results obtained in Example 1. A current standby graph as a function of potential, in which the sample S 2 containing iron was analyzed. Fig. 6 shows a graph of current characteristics as a function of potential obtained in Example 1, in which a sample S 3 containing gold was analyzed. Fig. 7 shows a current characteristic graph obtained as a function of the potential obtained in Example 2, in which a sample S 4 containing copper was analyzed. Fig. 8 shows a current characteristic diagram as a function of potential obtained in Example 3, in which a sample S5 containing an alloy or brass was analyzed. Fig. 9 shows the current standby characteristic obtained as a function of the potential obtained in Example 4, in which a sample S6 composed of many metal elements was analyzed. Fig. 10 shows a current standby graph obtained as a function of the potential obtained in Example 5, in which a sample S 7 or a 100 yen coin was analyzed. Figure 11 shows the current standby characteristic obtained as a function of the potential obtained in Example 5, in which a sample S8 or a 500 yen coin was analyzed. Figure 12 shows the current characteristics as a function of potential obtained in Example 5, in which sample S9 or a 25-cent (one-quarter dollar) coin was analyzed. The current characteristic diagram as a function of the potential obtained in Example 6 is shown in Section 13 (3), in which a sample S1Q or a 100 yen coin is analyzed. Figure 14 shows the current characteristics as a function of potential obtained in Example 6, in which sample S11 or a 1-cent (10-cent) coin was analyzed. Figure 15 shows the current characteristic diagram as a function of potential obtained in Example 7, in which -17 including 1 X 1 (Τ6 Μ P b (Ν 0 3) 2) is analyzed.-This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) ------------- · I ------ • 丨 Order -------- line 丨 (Please Read the precautions on the back before filling this page) 528867 A7 B7 V. Description of the invention (16) Sample solution S 1 1. Figure 16 shows the current characteristic diagram as a function of potential obtained in Example 8. Among them, the sample solutions S 1 2-S 1 6 containing different amounts of Pb (N03) 2 are analyzed. Figure 17 shows the values of the peak currents based on S12-S16 in Figure 16 after correcting the contribution from the background current. Standard measurement_response graph. Fig. 18 shows the current characteristic graph as a function of potential obtained in Example 9, in which a sample solution S containing 1 X 1 (Γ6 M cb (N 0 3) 2 was analyzed 17. Figure 19 shows the current characteristic diagram as a function of potential obtained in Example 10, in which sample solutions S 1 8-S 2 2 containing different amounts of Cd (NO 3) 2 were analyzed. Figure 20 shows the standard measurement-response graph based on the peak current of S18-S22 in Figure 19 after correcting the contribution value from the background current. Figure 21 shows the results obtained in Example 11 A current characteristic diagram as a function of potential, in which a sample solution S 2 3 containing 1 X 1 0_6 M Z n (N 0 3) 2 was analyzed. Figure 2 2 shows the results obtained in Example 12 A graph of current characteristics as a function of potential, in which the 'r sample solution s 2 4 containing 1 X 1 M H Au C 1 4 was analyzed. Figure 23 shows the results obtained in Example 13 as a function of potential A current characteristic diagram in which a sample solution S 2 5 containing 1 X 1 (Γ6 Μ P b (N 0 3 > 2) is analyzed. Fig. 24 shows the obtained as a function of the potential in Example 14 -18- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ·· ---- ---- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 A7 B7 17 V. Description of the invention () The current characteristic diagram, which includes 5X 1 (T7 M Cd Pb ion sample solution S 2 6. (Please read the precautions on the back before filling out this page) Figures 2 and 5 show the current standby graphs as a function of potential obtained in Example 15 in which the analysis A sample solution S 2 7 containing IX 1 (Γ6 M Cu (N03) 2. Fig. 26 shows the current characteristic diagram as a function of the potential obtained in Example 16 in which sample solutions S 2 8-S 3 2 containing different amounts of Cu (N03) 2 were analyzed. Fig. 27 shows a standard measurement-response graph based on the peak currents of S28-S32 in Fig. 26 after correcting the contribution value from the background current. Fig. 28 shows the current standby characteristic obtained as a function of the potential obtained in Example 17 in which the sample solution S 3 3 containing different metal ions is analyzed. Fig. 29 is an electrochemistry using a conductive diamond electrode. The schematic diagram of the analysis system (flow injection system) shows an embodiment of the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 30 is a graph of the current characteristics obtained using the electrochemical analysis system representing one embodiment of the present invention. At this time, 20 microliters of 100 # M NADH were compared with 1 minute intervals. 0.1 M phosphate buffer was repeatedly injected into the system through an injection valve. Figures 3A, 31B, and 31C are graphs of current characteristics obtained using an electrochemical analysis system representing an embodiment of the present invention. At this time, 2 Q microliters of 100 # M, 100nM, or 50nM NADH were used at 1 minute intervals. Repeated injections with 0.1M phosphate buffer through the injection valve into the system. -1 9- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 Α7 Β7 V. Description of the invention (18) (Please read the precautions on the back before filling this page) Figure 32 is 20 μl of 10 # M NADH (in 0 _ 1 phosphate buffer) was injected into the system at 0.5 ml / min. The graph of the potentials related to potential was obtained. Figure 33 plots the voltage − One of the current characteristics was obtained from an electrochemical analysis using a conductive diamond electrode, and the other was obtained from the same analysis using a conductive glass sulphur electrode. These analyses were performed at 0.1 μM buffer (pH It was performed with 100 #M histamine in 7). Fig. 34 shows a current standby graph obtained by using an electrochemical analysis strip showing an embodiment of the present invention. At this time, 100 A histamine was repeatedly injected into the strip at 1 minute intervals. 35A35 is a current characteristic diagram obtained by using an electrochemical analysis system showing an embodiment of the present invention. At this time, 20 microliters of 50 M, 20 # M, 10 / uM, and 1 # M histamine were Repeated injections into the system through injection valves at minute intervals. Figure 3 5B shows a graph involving histamine concentrations with peak currents. Figure 36 compares the potential range obtained from conductive diamond electrode, glass sulphur electrode, platinum electrode and gold electrode at (K 5 M sulfuric acid (in water). Printed by Figure 3 7 printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs It is a schematic diagram of a uric acid sensor, showing one embodiment of the present invention. Figure 38 is a schematic diagram of a uric acid analysis system, showing one embodiment of the present invention. Figures 3 and 9 show analysis of uric acid and Results of samples of ascorbic acid. -2 0-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7 V. Description of the invention PD is in the same way as the picture. It is taken as the flow chart. The result is that the B is passed through the product 0. The attempt is to measure the quantity of Ampere, the normal voltage, and the non-pulse. Give the picture Figure 1 2 4 4 The best way to the background scene. 0 The flow diagram of the electrical time meter should jump to the bit level. The electrolysis is excessively passed. When the electricity is output C, the map is graphically jumped to 43 steps. flow The electric travel can not be changed from 1 to 3. In the figure, it should be 0. ^ Η Quantitatively calculate the quasi-current electricity and get the urine out. Give it to the picture. Figure 4 5 4 4 From the acid connection, the blood electrode maps the primary electric resistance stone and the steel. The acid gold to the urine is contained in the lead and is covered with the best electric sample. The steel electrode that has just arrived at the gold electrode is shown in Figure B 6 4 And A 6 4 are connected to and with \ 1/0 Figure} 6A Figure 4 B Figure 46 < Figure 〈Characteristic diagram〉 Characteristic current analysis of the electrolysis of the electrolysis of the acid after the urination of the oxygen before the anode and the sum of the positive (Please read the precautions on the back before filling in this page) Oxygen pole anode accepts 47 poles of electricity. Stone rigid Rigid current is conductive and precipitates to the acid map blood 7B bad IX anti line 47 goes to the first And the figure below shows the value of the peak time electric current of the bitmap electric current or the peak value of the peak. The oxygen will be extremely positive. The figure is printed and analyzed by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The jet flow is based on the graphic representation of the special current. The given example is shown in Fig. 9 L 4 〇 with the best results. The Lai Lei coated stone boron ribbed doped auxiliary ceE ionization is equal to the multi-conductivity of the membrane stone diamond body crystal with / IV pressure. The rate is 33 frequencies (1 The DVDC CV assists the communication when the pressure is applied. The auxiliary body is a multiple of several times such as the pressure of the sub-force, such as the communication 0. The system is τ wave. The micro paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention Γ) The following uses a microwave CVD film preparation device provided by AST e X. A silicone substrate {S i (1 G 0)} was used. The substrate is textured (for example, polished with diamond powder of 0 · 5 # in particle size) and then placed in place in a substrate holder. Materials used for film formation include a mixture of propylene and methanol (volume ratio of 9 ·· 1), and boron oxide (B 2 0 3) is added thereto to obtain a boron / carbon ratio (B / C ratio) of 10 4 ppm mixture. The pure krypton 2 gas used as a carrier gas is passed into a cavity from the material for film formation, and the cavity is also filled with hydrogen gas through another line (for example, a flow rate of 5 3 2 ml / min) to obtain a specific pressure ( For example, 1 1 5 X 1 3 3. 3 2 2 P a). Then, a microwave of a frequency of 2.4 5 H G ζ was applied for discharging, and the power was adjusted to 5 kW. After stabilization, Η 2 gas used as a carrier gas was passed through the material (liquid) used for film formation. Film formation is performed at a rate of 1-4 a Η 1 / hour. The duration of film formation was adjusted to obtain a film with a thickness of about 30 A ffl. The device does not need to intentionally heat the substrate, but in normal operation, the substrate is heated to about 8500-95 ° C. In this way, a polycrystalline diamond film (hereinafter referred to as a conductive diamond electrode) doped with boron (B 3) was prepared. Its Mann spectrum has a single peak at 1333 cm 4 and no activity at 1 400-16 cm 4, indicating the presence of amorphous carbon. Its electrical conductivity is about 1 (Γ3 U · cm, and the cyclic voltmeter chart obtained in 0.5 Μ Η 2 S 0 4 shows that it has a wide range of potentials-1.2 5 to + 2 · 3 V (compared to S Ε Ε). The analysis of solid gold ray using the analysis of lead gold Ⅰ stone mine pole coke system uses the analysis system shown in Figure 1, where the conventional active electrode has been The invention is replaced by the conductive diamond electrode. The electrolyte is 0.1 M-22- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -----,-一 ---- -—----- ^ — Order -------- (Please read the notes on the back before filling out this page) 4 528867 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ( /) KC1 (reagent grade) composition, the pH value has been adjusted to pH 1 by adding HC1 (reagent grade) ^ using a potentiostat (HZ3000 type, by Hokuto

(Provided by Electric Co.). A conductive diamond electrode was inserted into the analytical strip so that its sharp surface area immersed in the solution was 0.4 cm 2. Unless otherwise specified, measurements are performed at room temperature. (Example 1) Analysis was performed using a sample S1 containing solid lead (99% purity). First, simply rub the conductive diamond electrode with the sample 2-3 times by hand, so that part of the sample is transferred to the surface of the electrode. The adhesion of the sample to the surface of the conductive diamond electrode can be checked by SEM: the sample invades the space between the fine crystals on the surface of the electrode, but the amount of adhesion is very small (estimated several nanograms). The conductive diamond electrode is then placed in the analysis strip. For the differential anode stripping voltmeter method, the potential of the conductive diamond electrode relative to the reference electrode is gradually shifted from the negative side to the positive value side at a scan rate of 20 fflV / s. That is, through this step, the sample adhered to the surface of the conductive diamond electrode is dissolved in the electrolyte, and then the current change in response to the potential step is measured to obtain a current characteristic diagram (differential pulse volt-ampere diagram). In order to analyze the sample S1, the peak current attributed to the test object was read from the current characteristic chart, and the potential at which the peak current appeared was measured. In another operation, a sample composed of solid iron (99% purity) was measured under the same conditions as above. That is, the split sample S 2 is transferred to the surface of the conductive diamond electrode by friction, and then dissolved in a solution for analysis. In another operation, under the same conditions, the determination of solid gold (9 9.9 5¾ -23- this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I --------- --------— I --- 1 ----- (Please read the precautions on the back before filling this page) 528867 A7 _B7_ V. Description of the invention f) Purity). That is, a part (very small amount) of sample S 3 is transferred to the surface of the conductive diamond electrode by friction, and then dissolved in a solution for analysis. The analysis results of the samples S 1, S 2 and S 3 are given in the current characteristics diagrams 4, 5 and 6, respectively. As shown in Figure 4, a clear peak was obtained at a potential of -0.48 V, indicating that the sample S 1 was composed of lead. Referring to Fig. 5, a clear peak was obtained at a potential of 0.8 V, indicating that the sample S2 was composed of iron. Referring again to FIG. 6, a clear peak is obtained at a potential of about 0.95 V, indicating that the sample S 3 is composed of gold. The width of the peak current (half-peak width of 0.3 V or less) of the sample S 1 as shown in FIG. 4 is larger than that of the sample S 2 as shown in FIG. 5. This difference in current width can be explained by the rapid dissolution of sample S1 into solution relative to sample S2. In this embodiment, it can be confirmed that solid matter, particularly solid metals, including lead, iron, gold or the like can be measured based on the analytical system of the conductive diamond electrode of the present invention. In addition, the system is applicable even for the determination of metals such as gold having a relatively high oxidation potential. (Please read the precautions on the back before filling this page) _ WU printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which dissolves copper and passes oxygen through, as in the example} Gold 2 I Oxygen 7/1 \ / 1 Progressive reaction} In the reverse reaction, oxygen can be moved in steps according to the steps of CU, one, three times through the cause 1) 〇 copper KC set ί, stable as a step ί chase Rotary and rechlorinated degree shows high concentration of concentrated chlorine meter. ③ The solution of liquid electrolyte is passed. Ο This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7. 5. Description of the invention (23)

In contrast, if copper is dissolved in an electrolytic solution without chlorine radicals (or an electrolyte solution with a very low concentration of chloride radicals) by gasification, the gasification is performed according to the above reaction formula (oxidation in one step). In this example, a sample S4 composed of solid copper was used. A part (very small amount) of sample S4 was adhered to the surface of the conductive diamond electrode, and then dissolved in an electrolyte (having a very high concentration of chloride) for analysis. The analysis result of the sample S 4 is given in FIG. 7. As shown in Figure 7, three peak currents can be observed at different potentials, indicating that sample S 4 is composed of copper. In this example, it can be confirmed that solid matter, especially solid metal (e.g., copper) subjected to multi-step oxidation can be determined based on the analysis system of the conductive diamond electrode of the present invention. (Example 3) In this example, a sample S 5 composed of an alloy, that is, brass (composed of 65% copper and 35% zinc, Nilaco) was used. A part (very small amount) of sample S 5 was adhered to the surface of the conductive diamond electrode, and then dissolved in an electrolyte (having a very high concentration of chloride) for analysis. The analysis results of sample S 5 are given by the current characteristics. Figure 8 shows that as shown in Figure 8, three peak currents can be observed at the potentials-(K 8 5,-0.0 2 and 0.4 2 V. Out Now the peak current of -0.85 V can be attributed to the rate of adhesion of the oxide (Z η / Z n +) dissolved in the solution. The peak currents appearing at-0. 0 2 and 0.4 2 V are close to each other May be oxidized -25- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order j -------- line | Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 Α7 Β7 2 4 V. The copper contained in the adhesive of the invention description (). This shows that sample S 5 is made of zinc and copper The reason for the above two peak currents of copper can be explained as that C τι + can be stabilized by conversion to chloride: Copper contained in the adherent is gasified in two steps (C u ◦ Cu and Cu + — C u 2t). In this embodiment, it can be confirmed that the solid matter can be measured based on the analysis system of the conductive diamond electrode of the present invention, and in particular Alloys containing various metals, such as brass, and alloys containing many metals, the corresponding contributions of these metal components, and interactions can be analyzed. It has also been found that the analytical system of the present invention can be used to determine copper containing multiple steps of oxidation (Example 4) In this example, a sample S 6 composed of an intermetallic compound including zinc, cadmium, lead, aluminum, aluminum, nickel, and chromium was used. Part ( Very small amount) Sample S 6 is adhered to the surface of the conductive diamond electrode, and then dissolved in the electrolyte for analysis. The analysis result of sample S 6 is given by the current characteristics. Figure 9 shows σ as shown in Figure 9 at different potentials. There are several peak currents. Based on the potential that produces the peak current, it can be confirmed that sample S 6 contains zinc, zinc, lead, aluminum, cobalt, nickel, copper, and chromium. From this, it can be confirmed that the conductive diamond electrode-based system can be analyzed (Example 5) In this example, samples S7, S8, and S9 are used: Samples S7 and S8 are silver in appearance but are made of copper-nickel alloy (75% copper and 25%). nickel ) Yen hard -26- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------: 1 Order _ · -------- Line 'Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 A7 --- 5. Description of the Invention (25) (Please read the precautions on the back before filling this page) (1G0 yen coin and 500 yen coin respectively); Sample S9 is a 25 US dollar coin (a quarter dollar coin) made of a copper-nickel alloy containing 8.33% by weight nickel. Partial (very trace) samples S 7-S 9 were adhered to the surface of the conductive diamond electrode and then dissolved in the electrolyte for analysis. The analysis results of samples S 7-S 9 are given by the current characteristics in Figs. In Figures 10 and 11, the peak current appears at the same potential. From this, it can be confirmed that the samples s 7 and S 8 have the same composition. In contrast, the peak currents in Figure 12 are different from those in Figures 7 and 8. To explain why, a 100 yen coin (or a 500 yen coin) has a composition different from that of a quarter dollar coin, and the two coins may be manufactured using different processes. (Example 6) In this example, samples S 1 0 and S 1 1 were used: Sample S 1 0 had a brown appearance and was made of bronze (95% copper, 3-U zinc, and 1-2% tin) Japanese yen coin (10 yen coin); sample S11 is 1 US dollar (1G cent coin) made of copper plated on a zinc substrate. The split (very small) samples S 1 0 and S 1 1 were adhered to the surface of the conductive diamond electrode, and then dissolved in the electrolyte for analysis. The analysis results of the samples S 1 0 and S 1 1 were printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Electricity and Economics in order to form a group of gold coins for use in electricity. Guidance can be hardly the same as if the status is not the basic example of electricity and the United States. This is not the same as the art certificate. In the same job, the currency is not created. It can be hard to create an incumbent. Use the analysis of the 27 C value to extract the points _ out of the peak element due to the Japanese yen, use 10 in the figure to fit the 14 figure, the species and the 14 due to two 5 13 and the 13th interpretation of the original example and The application of the polarity solution is true, such as Shiliu. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 B7 V. Description of the invention γ) Identification of real coins and fake ones coin. (Please read the precautions on the back before filling this page) As mentioned above, the electrochemical analysis method based on the conductive diamond electrode as the first aspect of the present invention can analyze with high accuracy and sensitivity whether it is made of inert metals and alloys Test object. In addition, since this kind of system only needs a very small amount (nanogram) of test objects during analysis, the original test object can be kept intact (non-destructive analysis). The diamond electrode is not limited to any pending form, or may take any form as needed, as long as it is suitable for obtaining a part of the test object by friction.的 Analysis of the Lightning Chrysanthemum Using the Analysis System of Lei Jinguo Shi Lei Pole The analysis system shown in Fig. 1 is used, in which the conventional active electrode has been replaced with the conductive diamond electrode of the present invention. This system is applicable to the analysis of electrochemical activity test objects in solution. The analysis includes: using a conductive diamond electrode as the active electrode, placing the active electrode and the counter electrode in a solution containing the test object, and then scanning the potential of the active electrode from the original value to a negative value, so that the electrochemical activity test object is plated to the activity On the surface of the electrode. Then, the potential of the active electrode is gradually scanned to a positive value, so that the plating test object is decomposed into the solution, and at the same time, the ionization change in response to the potential step is detected to analyze the electrochemical activity test object. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Example 7) In this example, sample S12 was used with 1 X 1 (T6 Μ P b ( Ν 0 3) 2. The analysis process includes: scanning the potential of the conductive diamond electrode to a negative value (relative to the reference electrode), and then holding the potential at -1.0V for 2 minutes, so that the sample solution S12 -28- this paper size applies China National Standard (CNS) A4 Specification (210 X 297 mm) 528867 Printed by A7 B7_, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention Pb ions (Pb2) are electroplated on the surface of conductive diamond electrodes. This results in P b deposits. Then, the potential of the conductive diamond electrode is gradually changed to a positive value at a scanning rate of 10 G in V / s (a height of 100raV and a duration of 50ras in looms) through a uniform pulse. The test object on the diamond electrode is dissolved in the solution, and the current change in response to the potential step is detected at the same time. The analysis results are shown in Figure 15 of the current characteristics. As shown in Figure 15, a significant peak was obtained, and the potential reading for the peak current indicated that the sample electrolyte S12 contained Pb ions. (Example 8) In this example, different amounts of Pb (NO3) 2 were dissolved in 0.2M acetate buffer (PH value 5) to prepare samples S13-17: at 0.2M acetate In a buffering agent (with a pH value of 5), S 1 3 contains 2 · 0 X 1 (Γ6 Μ

Pb (NO 3) 2, S14 contains 1.6X 1 (Γ6 M Pb (NO 3) 2, S15 contains 1 · 2 X 1 Μ P b (N 0 3) 2, S 1 6 contains Q. 8 X 1 (Γ6 Μ

Pb (NO a) 2. S17 contains 0.4X 1 (Γ6 M Pb (NO 3) 2. The analysis process includes: scanning the potential of the conductive diamond electrode to a negative value (relative to the reference electrode), and then holding it at -1 · QV At a potential of 5 minutes, the Pb ions (Pb 2) in the sample solution were electroplated on the surface of the conductive diamond electrode to generate Pb deposits. Then, a pulse was passed through the column at a scan rate of 100 m V / s. (The height is 100mV, and the duration within 100ms is 50ms.) The potential of the conductive diamond electrode is gradually changed to a positive value side, so that the gold can be deposited on the 9-2. This paper scale applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) -----.—----- Installation 丨 ----- ^ — Order · ---------. (Please read the precautions on the back first (Fill in this page) 528867 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs B7__V. Description of the invention (28) The test object on the diamond electrode is put into the solution, and the current change in response to the potential step is detected. The analysis results are shown in The current characteristics are shown in Figure 16 ^ As shown in Figure 16, a clear current peak is obtained, indicating the sample electrolyte S 13-S17? 1) Ion. Figure 17 shows the standard measurement-response curve after the background currents appearing at each peak current (S13-S17) are corrected. From the standard metering-response curve in Figure 17, it can be confirmed that the height of the peak current (S 1 3-S 1 7) increases in proportion to the concentration of P b (N 0 3) 2 in the sample solution. (Example 9) In this example, sample s18 was used, and 1 X 1 M Cd (NO 3) 2 in 0.2 M acetate buffer (pH 5). The analysis was performed in the same manner as in Example 7 above. The analysis results are given in section 18 圔. As shown in FIG. 18, a significant peak is obtained, and the potential reading when the peak current is obtained indicates that the sample electrolyte s 1 8 contains cd ion (Cd 2) 〇 (Example 1 〇) In this example, the Different amounts of Cd (N03) 2 were dissolved in 0.2M acetate buffer (pH value 5) to prepare samples S19-23: in 0.2M acetate buffer (PH value 5), S19 contains 2 · 0 × 1 (Γ6Μ Cd (N03) 2, S20 contains 1 · 6 × ir6 M Cd (N03 > 2, S21 contains 1 · 2 X 1 〇 · 6 MC d (N 0 3) 2, S 2 2 contains 0 · 8 X 1 (Γ6 Μ Cd (N03) 2, S23 contains 0.4 × 1 (Γ6 M Cd (H03 > 2. The analysis is performed in the same manner as in Example 8 above. The analysis results are in the current characteristics -30-( Please read the precautions on the back before filling this page) _% I--_ Line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7 V. Description of Invention (29) Figure 19 shows β as shown in Figure 19, which shows a significant peak current, which represents the Cd ions in the sample electrolytes S13-S17. Figure 20 shows the peak currents (S 1 9-S 2 3) The standard measurement-response curve after the field current. From the measurement-response curve in Figure 20, it can be confirmed that the height of the peak current (S 1 9-S 2 3) and the concentration of C d (H 0 3) 2 in the sample solution It is proportionally increased. (Example 1 1) In this example, sample S 2 4 was used, and 1 X 1 Ο # Μ Zn η (ΝΝΝΑ) in 0.2 M acetate buffer (pH value 5). 0 3) 2. The analysis process includes: scanning the potential of the conductive diamond electrode to a negative value (relative to the reference electrode), and then holding the potential at -1.3V for 10 minutes, so that Pb ions in the sample solution are plated onto the conductive diamond electrode. On the surface, Zn deposits are generated here. Then, a potential pulse (height of 100inV and duration of 100ms within 50ms) is passed at a scanning rate of lQOniV / s to gradually change the potential of the conductive diamond electrode to a positive value, In this way, the test object deposited on the diamond electrode can be dissolved in the solution, and the current change in response to the potential step can be detected at the same time. The analysis result is shown in Figure 21 of the current characteristics. As shown in Figure 21, an obvious result is obtained. Peak, indicating sample electrolyte S 2 Z Γ1 ion in 4. (Example 12) In this example, a sample S 2 5 was used, and IX 10-6 M HAuC14 in aqua regia (composed of 0.1 M H C 1 and 0.3HHN03). The analysis process includes: scanning the potential of the conductive diamond electrode to a negative value (relative to the reference -31- this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm)) (Please read the precautions on the back before filling (This page) ------- I-Order * -------- Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 A7 B7 V. Description of the invention θ) (Please read the note on the back first Please fill in this page again) and then hold the potential at -1. Ο V for 6 QG seconds, so that the Au ion in the sample solution is plated on the surface of the conductive diamond electrode, where Au deposits are generated. Then, the potential of the conductive diamond electrode was gradually changed to 100 mV / s through a uniform pulse (with a height of 100 m V and a duration of 50 in s in 100 ία s). Positive potential, so that the test object deposited on the diamond electrode is dissolved in the solution, and the current change in response to the potential step is detected at the same time. The analysis results are shown in Figure 22 of the current characteristics. As shown in Section 22 (2), a significant current peak was obtained, and a potential reading of the peak current indicated that the sample electrolyte S25 contained All ions. (Example 1 3) At present, the Metropolitan Water Distribution Bureau limits the concentration of Pb ions in tap water to 2.4X1 (Γ7 Μ (50 micrograms / liter) or lower, while the urban water distribution in West Virginia, USA In general, the value is limited to 1.8 X 1 (Γ7 Μ (3 7.9 micrograms / liter) or lower. In general, ICP or atomic absorption spectroscopy can determine the Pb ion concentration in tap water on the order of 10 7 Μ. However, this method requires high cost and time. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs in order to check whether the system of the present invention can be used to analyze low-concentration P b ions, the sample S26 was used in this example. 1 X 1 (Τ9 Μ P b (H 0 3)) in 1M KC1 (pH 1) 2. The analysis process involves scanning the potential of the conductive diamond electrode to a negative value (relative to the reference electrode), and then at -1. Hold the potential at 0V for 15 minutes, so that the Pb in the sample solution-32-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 528867 A7 B7 3 1 V. Invention Ming () ion plating on the surface of the conductive diamond electrode, where P b deposits are generated. Then, a uniform pulse (height 100 m V, within 100 in s) is passed at a scanning rate of 2Q0 HIV / S. The duration of time is 50 ms), the potential of the conductive diamond electrode is gradually changed to a positive value side, so that the test object deposited on the diamond electrode is dissolved in the solution, and the current change in response to the potential step is detected at the same time. The analysis results are shown in Figure 23 of the current characteristics. As shown in Figure 23, a clear peak is obtained, which represents the P b ion in the solution. From this, it can be confirmed that the present invention can easily analyze P b at a low cost. Ions, even if Pb ions are present in the electrolyte at a very low concentration (or, for example, in tap water). (Example 14) In this example, sample S 2 7 was used at 0.1 M KC 1 (p 5 X 1 (Γ7 MC d and P b ions in which the value is 1), and the value of ρ 已 has been adjusted to ρ 1 by adding HC 1. The analysis is performed in the same manner as in Example 8 above. The analysis results are in the current characteristics. It is given in Section 24. As shown in Figure 24, in Two obvious current peaks were observed at the same potential, and the potential reading when the peak current was obtained indicates that the sample electrolyte S 2 7 contains C d and P b ions. It can be confirmed that even if the sample solution contains multiple metal ions, The system of the present invention can also determine these metal ions separately from each other. (Example 15) In this example, a sample S 2 8 was used, and 1 X 10 $ M Cu (NO 3) 2 in 0.2 M acetate buffer (pH 5). According to the above implementation -33- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

528867 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 2 V. Description of Invention () Example 7 was analyzed in the same way. The analysis results are given in Figure 25. As shown in Figure 25, a clear peak is obtained, and the potential yield when the peak current is obtained indicates that the sample electrolyte S 2 8 contains Cu ions (Example 16). In this example, different amounts of Cu (N 0 3) 2 was dissolved in 0 · 2 M acetate buffer (PH value 5) to prepare sample S29 " " S33: In the buffer, S29 contains 2.0 × 11Γ6 M Cu (N03) 2. S30 contains 1 · 6 X 1 〇-6 HC u (N 0 3) 2. S 3 1 contains 1 · 2 X 1 (Te MC u (H 0 3) 2, S32 contains 0 · 8 × ΙΟ-6 M Cu (N03) 2, S33 contains 0.4 × 1 0— μ cu (N 0 3) 2. The analysis is performed in the same manner as in Example 8 above. The analysis results are given in the current holding graph in Figure 26. As shown in Figure 26 圔As shown, significant peak currents are obtained, representing Cu ions in the sample electrolytes S 2 9-S 3 3. Figures 27 show the corrections that occur at each peak current (s 2 9-S 3 3). Standard metering-response curve after background current. From the metering-response curve in Figure 27, it can be confirmed that the peak current (S 2 9-s 3 3 > height and Cu (N 0 3) 2 in the sample solution Increase in concentration In the diamond analysis results shown in Figures 25 and 26, only one peak current is obtained for Cu ions in the solution. However, if copper in the sample solution is dissolved in an electrolyte with a high concentration of chloride (high concentration of chloride ions) Then, cu + is gradually stabilized by conversion to chloride. Therefore, Cu can be gasified in a complicated manner represented by the following reaction formulas (1)-(3),

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I ------------- • —Order -------- line (please read the back first (Please note this page before filling in this page) 528867 A7 B7 V. Description of the invention θ)

Cu 0 4 Cu 2 (3) Three different peak currents are therefore generated. From this, it can be confirmed that, as long as the properties of the electrolytic solution are taken into consideration, the system of the present invention can analyze metal ions such as c ions that can undergo multi-step oxidation in the electrolytic solution. (Example 17) In this example, a sample S 3 4 was used, and 2 × 1 (T7M Zn, Cd, Pb, and Cu ions were contained in 0.1 M KC 1, and its pH value was adjusted to pH by adding HNO 3 1. The analysis process includes: scanning the potential of the conductive diamond electrode to a negative value (relative to the reference electrode), and then holding the potential at -1.2 V for 300 seconds, thereby electroplating Zn, Cd, Pb, and Cii ions in the sample solution Onto the surface of the conductive diamond electrode, where Zn, Cd, Pb, and Cu deposits are produced. Then, a uniform pulse (height 100inV, with a duration of 100ms is passed at a scan rate of 200 m V / s is 50ras), the potential of the conductive diamond electrode is gradually changed to a positive value, so that the test object deposited on the diamond electrode is dissolved in the solution, and the current change in response to the potential step is detected at the same time. The analysis results are shown in Figure 28 of the current characteristics As shown in Figure 28, several current peaks can be observed at different potentials, and the potential readings when the current peaks are obtained indicate that the sample electrolyte S34 contains Zn, Cd, Pb, and Cu ions. It can be further confirmed , And can only analyze Metal ions in the liquid, that is, when the potential of the diamond electrode is scanned to a negative value, the potential is limited to a certain range for transformation, which can deposit the chemical on the diamond electrode. (CNS) A4 size (210 X 297 mm) (Please read the notes on the back before filling out this page) -I ..... n 3 —L n one δν 1- ^ 1 I 1 ϋ ϋ ϋ ϋ I -Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 34 V. Description of the invention () The chemical substances are limited to the metal ions in the solution. The electrochemical analysis method based on the conductive diamond electrode in the second aspect can be used to analyze the electrochemical separation activity test object with a wide range of oxidation potential. This analysis method can be very accurate and sensitive analysis (such as online monitoring) included in the solution (such as , Sewage or drinking water). Compared with the conventional analysis method using a sulphur sensor as an active electrode, the analysis method of this embodiment can analyze Very low concentration of electrochemically active materials. By adjusting the analysis conditions, the analytical method of this embodiment can also be used to analyze electrochemically active materials such as Cu ions as described in Example 16, which are very difficult to perform simple analysis. The analysis can also be limited to the target electrochemically active substance in solution. The analysis method of this embodiment can also be used to analyze metal ions (such as Au ions) with a higher oxidation potential. In the above embodiments, only the One or more metals, but the analysis method of the present invention is obviously applicable to the analysis of various electrochemically active substances contained in a solution (eg, agrochemicals, environmental hormones, etc.). In addition, the conductive diamond electrode used in the analysis system of the present invention is not limited to any specific form, or any form may be adopted as required. Anode argon of diamond thunder maple The anode gasification process of conductive diamond-coated electrodes involves placing the diamond electrode in a 0.1M KOH solution and then applying a voltage of 2.4 V (relative to SCE) for 75 minutes. In this operation, if necessary, use -3 at Q.1V / sec. 6-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page )

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 A7 B7 35 V. Description of the Invention () Scan the voltage three times at a rate of 0 · 1M KO Η solution, from + 4 V to "V (relative to SCE), and then keep the voltage at 4V 1 minute. In the above embodiment, 0.1M KOΗ was used. However, it can be replaced with ΐ2 S04 solution or HC104, or any other solution capable of anodizing on the diamond surface (for example, (NHO 3, HC1 or alkaline solution such as NaOH). Flow-cell-based analysis of organic compounds using a diamond mine pole. Figure 29 shows an electrochemical analysis system showing an embodiment of the present invention. Flow cell with conductive diamond electrode. In the figure, 11 indicates a buffer tank for storing buffer; 12 is a pump for liquid chromatography; and buffer tank 11 and pump 12 constitute a buffer. Agent guide device. The injection valve 13 is used to inject a sample into a flow cell 14 including a counter electrode, an active electrode, and a reference electrode 15, 16, and 17. A potentiostat 18 is used to control / pick tide by the electrode Signal, analysis equipment An i 9 (personal computer or similar device) performs various analyses based on these signals. The two devices 18 and 19 constitute an analysis device 20. For an analysis system with a top configuration, the buffer is passed through the pump 12 by the buffer tank 1 1 is transferred to the flow cell 14 while the test object is injected into the flow cell 14 through the valve 13. This allows the sample solution containing the tide test object and the buffer to be directed to the flow cell 14. The analysis of each component of the sample includes : Apply a voltage between the active electrode 6 and the counter electrode 5 in the flow cell 14, and then process the resulting signal through the analysis device 20. After analyzing the test object, process the sample solution; clean the entire system; Re-analyze the next test subject Force II into the system, and then repeat the analysis until the end of -37- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the back (Please fill in this page again)

528867 A7 B7 __ 3 6 V. Description of the invention () Fully analyze the test objects in this column. (Example 18) (Please read the precautions on the back before filling out this page.) Through the injection valve 1 3, in a 1 minute interval, it will contain 20 deg j liters of 10 # dihydronicotamine adenine di A sample of nucleotide (^ 011) (in () .1 ^^ acid salt buffer) is transferred to the flow cell 14; then the ## current change during injection is measured. Then, as shown in Figure 30, each injection of @ # gets the same current characteristics, including the peak current of the sample when it enters the flow cell, and the drop value when the sample is subsequently removed. From this, it can be confirmed that the electrochemical analysis with the injection valve accurately analyzes the sample injected repeatedly through the 13mm. During the analysis, the potential step was set to 60 GinV (relative to Ag / AgC1) and the flow rate was 1 ml / min. (Example 19) A similar analysis was performed in the same analysis system, in which the NADH concentration was used. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs through the injection valve 13 in a 1-minute interval, samples containing 20 microliters of 1 # Μ, ΐοοηΜ or 50iiM NADH (in 0.1M phosphate buffer) will be transmitted. Into the flow cell 14; then measure the change in current at each injection. Then, as shown in Figures 3 1 (a), 3 1 (b), and 3 1 (c), a peak current can be obtained when the sample enters the flow cell for all concentrations used. During the analysis as above, the potential step was set to 6 GQniV (relative to Ag / Agcl) and the flow rate was 1 ml / min. It can be confirmed that this system can accurately analyze even the sample containing a very small amount of test objects ^ -3 8- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 528867 A7 B7 V. Description of the invention (w) It can also be clearly seen from Figures 30 and 31 that for this type of flow cell based on a conductive diamond electrode, cross-contamination with previous samples will not occur , And the same sample can get the same results when repeated analysis. This may be due to the very stable surface of the diamond electrode, which prevents the test object from sticking to it. That is, the test object leaves the flow cell after each measurement and does not stick to the electrode surface, which indicates that the conductive diamond electrode is not suitable for continuous analysis based on the flow cell of the present invention. (Example 20) Under the control of the pump 12, 20 microliters of 100 # M HADH (in a phosphate buffer with a pH value of 7 · 2) was injected into the analysis system of the present invention, and then Obtain the mutual correlation of current and voltage (voltaic ampere diagram). During this analysis, the flow rate was set to 1 ml / min. As a result, a graph A as shown in FIG. 32 is obtained. It can be confirmed from the graph A that the current is substantially saturated at 600 mV (relative to Ag / AgCl). Graph B in the same figure shows the voltammogram obtained when only the phosphate buffer was flowed into the analytical strip. From the results in Fig. 32, it can be confirmed that the system can analyze NADH, and it can be seen from the experiment that only phosphate buffer is flowed into the system that the conductive diamond electrode can obtain a very low background current. In general, for flow-cell based analytical systems, pulsations can have a significant impact on the results of an analysis. However, it can be seen from the results in FIG. 32 that the conductive diamond electrode can generate a very low background current. Therefore, the system of the present invention using this conductive diamond electrode is not greatly affected by the pulsation. -3 9- This paper size is applicable China National Standard (CNS) A4 Specification (210 X 297 mm) ---- 2 ---% ----- ^ --------- Order --- (Please read the note on the back first Please fill in this page again for matters) # 528867 A7 B7 v 38 V. Description of the invention () This can be analyzed more accurately than the conventional flow cell basic system. (Example 2 1) (Please read the precautions on the back before filling out this page) The analysis system of the present invention using a conductive diamond electrode as the active electrode is similar to other aspects except that the conventional system using a phosphate buffer as the active electrode Compare. The sample used was 100 #M histamine in a 0.1M phosphate buffer (pH 7). Figure 33 shows the linear scanning voltmeter plots for the two analyses (the correlation between current and potential). It can be seen that, compared with the conventional system using a glassy carbon electrode, the analysis system of the present invention using a conductive diamond electrode can effectively suppress the background current to a higher potential. For example, at 1 3 Q ϋ m V The background current (relative to SC E) is much lower, so the potential range is wider. In another operation, 5 0 # # histamine was used, and it was found that the signal / noise (S / B) ratio obtained by passing a conductive diamond electrode (even if the electrode did not undergo anode vaporization) was as high as 10 Times. (Example 2 2) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The histamine was continuously analyzed using the flow cell system of the present invention based on a conductive diamond electrode. At 1 minute intervals, transfer samples containing 20 microliters of 100 #M histamine (in phosphate buffer) to the flow cell 14; the voltage was set to 1.3V (relative to Ag / AgCl), -The flow rate is 0.5 ml / min. The results are given in Figure 34. From the results in Figure 34, it can be seen that the peak current can be reproduced with each injection of histamine, which indicates that the analysis of histamine can be guaranteed. -4 0- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 9 V. Description of the invention () That is, from these results can be It can be seen that the conductive diamond electrode introduced in the analysis system of the present invention is very effective for continuous analysis of histamine. (Example 23) A similar analysis was performed in the analysis system of the present invention, in which a lower concentration of histamine was used. Through the injection valve 1 3, the samples containing 20 microliters of 10, 20, and 50 # histamine (in a 0.1 M phosphate buffer) were transferred to the flow cell 14 at 1 minute intervals; Changes in current were then measured for each injection. Then, as shown in Figure 35 (a), for all concentrations, peak currents occur when the sample enters the flow cell. During this analysis, the potential step was set to 1 2 7 5 mV (relative to Ag / AgCl); the flow rate was 1 ml / min. In another operation, 100 A histamine was analyzed under the same conditions as above, and it was found that the peak current attributed to histamine was 4 3 7.0 9 6 HA. Figure 3 5 (b) shows the relationship between the peak current and the histamine concentration, which is obtained from the results of the first operation and the results of this operation shown in Figure 3 5 (a). It can be seen that the peak current is proportional to the histamine concentration, and the system can accurately analyze very low concentrations of histamine. (Example 24) The potential ranges obtained by using a conductive diamond electrode, a glass sulfonate electrode, a platinum electrode, and a gold electrode in a 0.5 M sulfuric acid aqueous solution were measured and compared. The results are shown in FIG. 36. It can be seen that the potential range obtained by a conductive diamond electrode is significantly wider than that obtained by a glassy carbon electrode, a platinum electrode, or a gold electrode. -4 1-—4. 丨 丨 (Please read the precautions on the back before filling this page) -14 I-I · —Line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 ___B7_ 4 0 V. Description of the invention () Determine the density of the residual current (current for charging the double layer) of each test electrode in the potential range. The residual current density obtained by the diamond electrode is tens to hundreds of n A / cm 2, while the corresponding density of other electrodes is about several # A / c m 2. The former is much lower than the latter. In addition, conductive diamond electrodes respond well to oxidants or reducing agents, and the current density increases as much as metal electrodes due to oxidation or reduction. (Example 25) The conductive diamond electrode was anodized, and then the electrode was installed in a flow cell of the analysis system of the present invention. The same analysis as above was performed using this statistic, and it can be seen from the results that this statistic is as effective or more effective than the aforementioned statistic in some types of analysis. It can also be seen that an analytical system using an anodized diamond electrode can obtain better results when combined with a liquid chromatography device than a similar analytical system using a simple conductive diamond electrode in other respects. From the above, it can be seen that the flow cell-based analysis system using a conductive diamond electrode can suppress cross-contamination between samples even during continuous analysis, obtain a very low background current, and is not particularly affected by pulsation. This is because diamond electrodes have a relatively large potential range compared to materials commonly used as sensor electrodes. In particular, a flow cell-based analysis system using an anodized diamond electrode can effectively analyze a variety of active substances continuously when combined with a liquid chromatography device. Analysis of anode argon 彳 h diamond thunder pole for beams Integrated urinary enzyme analysis-4 2-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -I n I n If II Ja ϋ IIIII (Please read the precautions on the back before filling this page) 'Order:-| Line_ Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy 528867 A7 B7 V. Description of the Invention Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy and printed as g Neutralize with quality gold. Dian Ming picked up by liquefaction? It is resistant to M when it is outside, and the white electric acid number is enough to dissolve the oxygen. 2 The acid has the condition. The egg guide urine sample coating can be polarized. Moreover, the selection of Zangyang must be prepared to analyze the companion thick 50 kinds of bands and the ai in the set of points required for the selection of electric steel products. 0-Because it is difficult to generate gold, the sample is good. The product should be 10 such as. The production of the instant device is determined to be based on the median value. The system is suitable for the example}, the oxygen is stable under the sense of independence. After taking the pole, the line P 条 can be divided into strips of liquid 1. The value of Qu is in analysing blood. W is a dilute effect. It depends on the acid and cation, and the pH is dissolved. The pre-acting acid can be used together with the pressed and soil-reduced soils, such as Changqing /, and the dialysis body to produce blood. The phase-opening electrode is acidic and polar, and the electric denaturation fluid is broken. Do not uric acid plus acid solubilization will be 3-acid and 0 --- 3 in the mass reactance. The electricians mentioned in the seeding area that the application letter is not the -4 pole urine urine P520 must-have products and organic acid coating it is this acid change coating rate. As far as electricity is concerned, in Η 必 必 必 必 感 感 感 will feel the urine coating as a face, the blood will speed the stone can be 1 sample of the acid /? F of the Ping Shao Xue analysis of stone analysis method 因: just tracing the c liquid value this just Due to urine f / acid-like reduction in acid content, the pH value of the four-phase anti-golden scan solution dissolves the pH, and the gold is, »1 urine can be learned as the near-current limit of urine and gold. For example, Θ is the acid-determining acid of the acid that is used for the analysis and release of the acid. Example: Utilization of 51-degree-diluted electrourinary polar blood for acidification to urinate peroxic constant electricity for urine selection. 2. Concentrated acid species. It can be used to destroy the blood and generate electricity. The analysis of the acid is based on the presence of acid. 2- Storage of urine. Yu Wei or Gang's resistance is determined by the gold test, low -----, ------- ¾ ----------- Order (Please read the precautions on the back before filling this page ) Line-·· This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 Α7 Β7 4 2 5. Description of the invention (), the solution containing uric acid can be alkaline, so use K. H or NaOH is used as the alkaline reagent. Urinary urinary sensor __ Figure 37 shows the outline of the uric acid sensor. The sensor includes a cavity 3 1 for receiving a cell body 30 of a sample solution 32, and has an active electrode 3 3 (its composition is described below), and a reference electrode and a counter electrode immersed in the sample solution 32 in the cavity 31. 3 4 and 3 5. The active electrode 3 3 is prepared as follows: An anodized diamond electrode 3 3 b is formed on the silicone substrate 3 3 a; the silicone substrate 3 3 is fixed to the connecting substrate 3 3 c; and then the connecting substrate 3 3 c is fastened to the tube 3 3 d; then the silicon gas alkyl material 3 3 a, the diamond electrode 3 3 b, and the head of the connection substrate 3 3 c and 3 3 d are coated with epoxy resin 3 3 e. fixed. Care must be taken during preparation to not apply epoxy resin 3 3e to the surface of the portion of the diamond electrode 33b that is in contact with the sample solution 32. The lead wire 36 is connected to the diamond electrode 3 3 b and then passes through the tube 3 3 d. The body is shaped like a box and sealed with a lid 37. Figure 3 8 of the analysis of urinary urinary tracts of Liangxian urine brewing decoction device is a diagram illustrating the analysis of the uric acid strip using a uric acid sensor. The same components as the uric acid sensor shown in Figure 37 are indicated by the same symbol. In FIG. 38, 41 denotes a uric acid transmitter, as shown in FIG. 37, and in the cavity 31 of the pool body 30 constituting the uric acid sensor 41, a sample solution 32 containing uric acid is placed. The uric acid sensor 41 is equipped with an active electrode 3 3, a reference electrode 34 and a counter electrode 35, and the electrodes 3 3, 3 4 and 3 5 send lead wires 36, 4 3 and 4 4 respectively. Lead wire 36, 4 3, and 4 4 guide signal control / -44- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Μ 丨 丨 ^% clothing (please read the precautions on the back first) (Fill in this page) 1 !! * 1 Order _i II II! Line. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 528867 A7 B7_ V. Description of the invention (43) The test section 4 5 is the potentiostat. The signal control / detection section 45 transfers the point signals received through the electrodes to an analysis device 46, that is, a computer, to analyze the target substance in the sample or uric acid in this case. (Example 2 6) Fig. 39 shows the differential pulse voltmeter (DPV) obtained when an anodized diamond electrode is used to analyze samples containing ascorbic acid and uric acid. In DPV, the absolute height of the potential (E i, η) changes, while the incremental height of the potential pulse (Δ E = E i, η-E s, η) remains constant, as shown in Figure 4G. In general, the incremental height of the potential pulse is maintained at 10-100 mV, the short electrolysis time At is 5-100ros, and the equalization time is 0.5-180 seconds. In addition, the current density is measured at two points: t s 1 or immediately after entering a potential step, and t s 2 or immediately after leaving a potential step. The difference in current density Δ i between these two points follows a function of the potential step height, and then the curve shown in Figure 41 is obtained. The current-potential curve thus obtained is called DP V. In the graph of Figure 39, the peak attributed to uric acid (ϋA) is sharp and distinct, while the peak attributed to ascorbic acid (AA) is broad and insignificant. It can be clearly seen that when using anodized diamond electrodes, uric acid can be clearly detected.结果 The results in Figure 39 were obtained from samples with a high concentration of ascorbic acid in addition to 50 a M uric acid. ⑵ A uric acid analysis method that can be used for actual measurements must be able to pick up uric acid in a very small number of samples. -45- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 4 ----:-Order ------- --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 528867 A7 ._B7_ 4 5 V. INTRODUCTION TO THE INVENTION (3) Therefore, the method of the present invention is used to detect uric acid in a very small amount of samples. (Please read the precautions on the back before filling in this page) (Example 2 7) Figure 4 2 shows the response characteristics obtained from a very small number of samples using an anodized diamond electrode (PSCA) using an anodized diamond electrode. . It is clear from this figure that the use of anodized diamond electrodes can clearly detect uric acid, which causes uric acid to be present in very small samples at very low concentrations. For example, this type of anodized diamond electrode can detect 50nM uric acid in the presence of 5 #M ascorbic acid (the concentration of ascorbic acid is 100 times that of uric acid). PSC Α is a method for observing the current-time response of potential steps: the potential is applied from an external circuit to a balanced electrode system; the balance is broken to generate an electrolytic current; the current disappears with time and is uncertain It reaches 0 for a long time, and obtains the current curve in response to the potential step in time. In Section 42 (2), curve a represents the measurement result of the 0.1 M HC 104 solution, curve b is from 5 # Μ ΑΑ + 0.1Μ HCl〇4, and curve c is from 5 # Μ ΑΑ + 0.1Μ HCl〇4 . The potential step is 0V-0.92V (relative to SCE). The potential step of 0.9 2 V (relative to S C Ε) comes from the peak of U Α, which can be confirmed from the data in Fig. 4-5. The sampling time is 500 m s. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 4 and 3 are the response characteristics of the background current obtained by PSCA. The test conditions are the same as in Figure 42. The data a, b, and c are basically not different, indicating the reliability of the test. Based on the data in Figure 4 and Figure 3, which show test reliability, the standard measurement-response chart shown in Figure 44 was obtained. In these measurement-response graphs-46- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 _B7_ V. Description of the invention (45), In the solid line, the sample does not contain anti-blood Results when acid; the broken line indicates the result when the sample contains 1 A M ascorbic acid in addition to uric acid, and the dotted line indicates the result when the sample contains 5 # Μ ascorbic acid in addition to uric acid. As can be seen from these measurement-response graphs, the method of the present invention can detect uric acid as low as about 0.7 nM. It can also be seen from these tests that the anodized diamond electrode can be used stably for a long time. Therefore, the diamond-coated electrode prepared as above can be reliably and stably used for routine analysis of uric acid in biological samples. Table 1 shows the concentration of uric acid in the biological samples (urine samples) actually used in the above experiments. In this table, A, B, C, E, F, and G list the concentration of uric acid in a urine sample from a man, and D and Η are from a woman's urine sample. It is clear from the concentration data in the table that the electrode in question can be used for the analysis of uric acid in biological samples. -----—----- Installation -------- Order ---------- ^ Awi (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs The paper size printed by the Bureau ’s Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 528867 A7 B7 4 6 5. Description of the invention () Table 1 Concentrate (mg / dl) A: male 3 3.9 B: male 5 6.61 C: male 3 9.4 D: female 15.1 E: male 3 4.2 F: male 4 0.3 G: male 7 0.5 female 10 2.5 (Example 2 8) In analyzing the effectiveness of uric acid in samples that additionally contain more or less ascorbic acid, the analytical strips using anodized diamond electrodes were compared to other similar strips but using simple conductive diamond electrodes. -4 8-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) ^ ------- ^ 1 Order * -------- line. (Please read the back first Note: Please fill in this page again) 528867 Printed by A7 B7_ 4 7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () In this example, a mixture containing 0.2 μm uric acid and lmM ascorbic acid is dissolved in (In K 1 MHC 104, a sample solution was obtained. Figure 4 5 shows a cyclic voltmeter chart showing the results of the analysis. In Figure 45, the discontinuous line indicates the results obtained with a simple conductive diamond electrode. The solid line indicates the results obtained with the anodized diamond electrode. The potential scan rate is maintained at IQOmV / s. The solid line curve in Figure 45 clearly shows that the use of anodized diamond electrode can change the uric acid. It is clearly distinguished from ascorbic acid. (Example 2 9) A similar comparison is made as follows: a strip with a simple conductive diamond electrode is used to analyze a sample containing uric acid or ascorbic acid, the electrode is taken out for anodization, and the anodized diamond The same electrode was used to analyze the same sample, and the results of the two analyses were compared. The test solution contains 50 # Μ ϋ A (in 0.1 MH HC 1 0 4, 4th 6 圔) or 50 # MA Α (in 0 · 1 Μ HC 1 0 4, Figure 4 7), the potential scan rate is maintained at 10fflV / s. Figure 4 6 A shows that samples containing only uric acid undergo anodization at the diamond electrode ^ The analysis results obtained previously, and the analysis results obtained after the anodization of the diamond electrode are given in Section 4 B 圔. Figures 4 7 A and 4 7 B show similar results, except that only ascorbic acid is used. Analysis of the sample. Refer to Section 4 6 A 6. Of course, a simple diamond electrode can get a peak. However, the same electrode after anodization can get a higher peak, which can be determined more accurately. When analyzing ascorbic acid, a simple diamond electrode Available at -49- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

528867 A7 B7 V. Description of the invention t8) 0 · 6 8 V EP (as shown in Figure 4 7 A) produces a significant current peak, (please read the precautions on the back before filling this page) and accept the anode gas There was no definite peak for the same electrode after chemical conversion. Therefore, if an anode chlorinated diamond electrode is used, uric acid can be clearly distinguished from ascorbic acid. In Figures 46A and 47A, UA and AA produce distinct peaks, but these peaks all appear at the same voltage 0.7V (relative to SCE) and overlap each other. Therefore, if a sample containing AA and ϋΑ is used for analysis, it is difficult to distinguish UA from ΑA in the sample, or it is impossible to distinguish between the two when the sample is very small. On the other hand, if the anodized diamond electrode is used instead, the results shown in Figs. 468 and 478, the voltages that produce the peak currents attributable to 0 纟 and 44 are transferred to each other. In particular, as shown in Fig. 48B, the anode vaporized diamond electrode does not produce a definite peak of ascorbic acid, while the simple diamond electrode does the opposite. As shown in Fig. 4 7 A, it produces a peak under the same conditions (at G.7V). Relative to SCE). It has also been found that anode vaporization can shift the potential at peak currents to 1.1 5 V (relative to S C E). From the above results, it can be seen that the concentration of UA can be determined independently of AA even when analyzing samples containing AA and ϋΑ using the anode gasified diamond electrode. (Example 30) In this example, in order to see how the voltage Eρ that produces the current peak attributed to uric acid and ascorbic acid changes with the pH value, a solution containing ϋΑ and ΑΑ is taken to change its PΗ value. And the voltage Eρ of the current peak of ascorbic acid follows DVP. The results are described with reference to Figure 48. As can be seen from the results in Figure 48, in fact, for the pH value of less than 7-5 0-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 528867 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed A7 B7 4 9 V. Description of the invention () There is an acidic range, except for the range of PH value less than 2. 70, uric acid and ascorbic acid can be distinguished, and the Ep of the current peak attributed to uric acid and ascorbic acid is reduced by The pH is separated from each other. Therefore, it can be said that for the analysis of uric acid, the sample solution should preferably be acidic, especially when the PΗ value is lower than 2.70, it can better distinguish uric acid from ascorbic acid. In addition, the sample should preferably have a pH value of 2 or less, and most preferably a pH of 1 or more, since uric acid and ascorbic acid can be more clearly separated during analysis. The lower limit of the pH value can be determined as needed, taking care not to damage the measuring device exposed to such a strong acidic solution. A flow cell-based uric acid analysis strip based on the anode gold chloride thunder pole was used to prepare a flow cell-based uric acid analysis strip that is basically the same as the flow cell-based analysis strip shown in Figure 29 (b), except that it uses an anodized diamond electrode as the activity. Electrodes instead of simple conductive diamond electrodes. (Example 3 1) A plurality of samples containing uric acid and ascorbic acid were analyzed using this flow injection-based analysis system, and the results shown in Fig. 4 to 9 were obtained. From this, it can be seen that this analysis system can be effectively used for the determination of continuous flow injection samples based on the peak current intensity attributed to UA and AA. The measurement conditions are as follows: the volume of the flow cell is 2 Q microliters; the mobile phase is 0.1M HCl 0 (pH 0.9) at a flow rate of 1 ml / min; injection of 500 nM UA or ΙαΜ ΑΑ; potential step Set at + G.93V (relative to Ag / AgCl). The results are shown in Figures 4-9. The current peaks generated by uric acid and ascorbic acid are significantly different from the current peaks obtained in the blank. Through this analysis, it can be seen that at a pH value of 0.9 in the range of pH less than 1, this -5 1-This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------- * 1 Order -------- ^ line (please read the notes on the back before filling this page) 528867 A7 B7 V. Description of the invention Γ) Consumers' Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs The printed flow injection analysis system with anodized diamond electrodes can even measure uric acid and ascorbic acid separately in the continuous analysis. As described above, 9 The diamond-coated electrodes that have been anodized according to the present invention can be combined in the same sample. Uric acid and ascorbic acid can be clearly distinguished for long-term temperature analysis 5 and m can detect very low concentrations of uric acid. In addition 5 people can easily determine the uric acid concentration of the sample on site regardless of whether it is skilled in the art. This string is based on the following 8 This patent asks: (1) Application No. 2 00-6 4 3 6 0, Submitted on March 9, 2000; ； Application No. 11 (1 9 9 9) Pain 14 9 1 4 3 1 9 Submitted on May 28, 1999 ( 3) Application No. Η 1 1 (19 9 9)-184525, 1 9 9 June 30 30 Θ Submit (4) Φ No. HI 1 (19 9 9)-19 5 1 7 3, 1 99 1999 7 Submit (5) application number HI 1 (19 9 9)-2 0 1088 5 1 9 9 July 9 Submit (6) application number HI 1 (19 99)-1 5 3 5 0 6 9 Submit ⑺ on June 1, 1989 Φ Please call HI 1 (19 9 9)-2 3 3 4 5 6 1 9 Submit on August 20, 1999, please call H1 1 (19 99)-2 0 4 3 94 9 1 9 9 Submitted on July 19, 2009. These 8 patent applications are incorporated herein by reference. The explanation of the symbols. 1 Analysis container 1 a Electrolytic solution lb Sealing film 2 Active electrode 3 Counter electrode 4 potentiostat -52- (Please read Note on the back, please fill in this page again) Order --------- The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7 V. Description of the invention f1) 4 a4 b55 a 5b 6 7 11 12 13 14 15 1617 18 19 2 0 3 0 3 1 3 2 3 3a 3 3b 3 3c 3 3d Potential scanner recorder reference electrode capillary lead feed tube stirrer buffer tank pump wide flow cell reference Electrode reference electrode reference electrode potentiostat analysis device analysis device cell body cavity sample solution polysilicon electrode anodized diamond electrode substrate tube -53- (Please read the precautions on the back before filling this page) ------- ί I --------- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 __B7 V. Description of the invention Γ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 3 e Epoxy resin 3 4 Electrode 3 5 Electrode 3 6 Lead wire 4 1 Uric acid sensor body 4 3 Bell wire 4 4 Feed line 4 5 Signal control / detection part 4 6 Analysis Hold Set A A ascorbic acid U A uric acid a curve b curve c curve SI sample

5 S Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Product Information Product Information Product Information Product Information Product Information (Fill in this page again.) · This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 528867 A7 B7. 5. Description of the invention. Intellectual Property Bureau of the Ministry of Economic Affairs.口 ΡΠ 品 品 品 品 PP PP products Sαρρ 品 口 PP0 products αππ samples sample samples sample samples sample samples (please read the precautions on the back first) (Fill in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

Patent No. 891 12888 "Electrochemical analysis method using conductive electrodes coated with diamond, and electrochemical analysis system based on it" (Amended on November 25, 91) 6. Scope of patent application: 1. An electrochemical analysis method using a conductive diamond electrode includes transferring a portion of the test object to the surface of the conductive diamond electrode by rubbing the surface of the test object against the surface of the conductive diamond electrode; immersing the conductive diamond electrode in an electrolyte; and conducting the conductive diamond The potential of the electrode is changed from negative 値 to positive 値, so the transfer test object can be dissolved in the solution; and the current change in response to the change in potential is detected, so the test object is analyzed. 2. An electrochemical analysis method using a conductive diamond electrode as described in item 1 of the scope of patent application, wherein the conductive diamond electrode is a boron-doped conductive diamond electrode. 3 · If the electrochemical analysis method using a conductive diamond electrode is used in item 1 of the scope of patent application, the potential of the conductive diamond electrode undergoes a potential step by the differential pulse voltmeter method, so that the transfer test object can be dissolved in in. 4 · If the electrochemical analysis method using conductive diamond electrodes is applied in the second item of the patent application scope, the potential of the conductive diamond electrode undergoes a potential step by the differential pulse voltmeter method, which can turn 528867. The test object is dissolved in the solution. 5. The electrochemical analysis method using conductive diamond electrodes as described in item 4 of the patent application scope, wherein the test object is a metal or an alloy. 6. A solution analysis method for an electrochemically active substance, including: using a conductive diamond electrode as the active electrode; placing the active electrode and the counter electrode in the solution; scanning the potential of the active electrode from the original electrode level to negative 値Therefore, the electrochemically active material is deposited on the surface of the active electrode by electroplating; the potential of the active electrode is gradually scanned to the positive electrode, so that the deposited material is dissolved in the solution; and the current change in response to the potential step is simultaneously detected , Analysis of electrochemically active substances. 7. The solution analysis method according to item 6 of the patent application, wherein the selective deposition of the target electrochemically active substance on the active electrode is achieved by limiting the negative threshold to the scanning potential of the potential of the active electrode. The solution analysis method of the sixth item of the patent application, wherein the conductive diamond electrode is a boron-doped conductive diamond electrode. 9. The solution analysis method according to item 7 of the patent application scope, wherein the conductive diamond electrode is a boron-doped conductive diamond electrode. 10. The solution analysis method of item 6 in the scope of patent application, wherein the potential of the conductive diamond electrode undergoes a pulsation 528867 driven by the differential pulse voltmeter method. 〇1 1 in solution · The solution analysis method according to item 6 of the application, wherein the electrochemically active substance is a metal. 1 2. A flow cell for electrochemical analysis, in which a sample solution is introduced; a voltage is applied between an active electrode and a reference electrode, thereby analyzing the sample solution; and then processing the sample solution; and repeating the above process for continuous electrochemistry The chemical analysis is characterized in that the active electrode includes a conductive diamond electrode. 13. The flow cell for electrochemical analysis according to item 12 of the scope of patent application, wherein the conductive diamond electrode is a boron-doped conductive diamond electrode. 14. The flow cell for electrochemical analysis according to item 12 of the scope of patent application, wherein the conductive diamond electrode undergoes anodization, which includes: the conductive diamond electrode is placed in an acidic or alkaline solution, and a sufficiently strong A current is applied to the conductive diamond electrode to undergo an oxidation reaction. 15. The flow cell for electrochemical analysis according to item 13 of the scope of patent application, wherein the conductive diamond electrode undergoes anodization, which includes: the conductive diamond electrode is placed in an acidic or alkaline solution, and a sufficiently strong A current is applied to the conductive diamond electrode to undergo an oxidation reaction. 16. An electrochemical analysis system, including 528867 6. A patent-application flow cell in which a sample solution is introduced; a voltage is applied between an active electrode and a counter electrode, thereby analyzing the sample solution; processing the sample solution; then Repeating the above process for continuous electrochemical analysis; and, an analysis device connected to the flow cell and controlling / detecting / analyzing signals from the flow cell, the system is characterized by a flow cell for electrochemical analysis For example, a conductive diamond electrode is used as the active electrode in item 15 of the scope of patent application. 17 · The electrochemical analysis system according to item 16 of the patent application scope, further comprising: a buffer guiding device for guiding the buffer to the flow cell; and, a sample injection valve for injecting the buffer guiding device And the flow cell, so the sample is directed to the flow cell after being injected through the sample injection valve. 18 · A method for uric acid analysis using anodized diamond-coated electrodes, comprising taking a solution containing uric acid as a solution to be tested; immersing a diamond-coated electrode that has undergone anodization with the counter electrode in the solution; A voltage is applied at a constant scan rate; and uric acid is selectively detected from a curve representing a change in an electronic signal generated by a diamond-coated electrode. 528867 6. Scope of patent application 19. For the uric acid analysis method using anodized diamond-coated electrodes, the test solution is acidic. 20. An anodized diamond-coated electrode obtained by the following steps: placing the diamond-coated electrode in an acidic or alkaline electrolytic solution, and then passing a sufficient amount of current to subject the diamond-coated electrode to oxidation The reaction is therefore anodized on the electrode. 2 1. The anodized diamond-coated electrode according to item 20 of the application, wherein the acid solution contains h2so4, hcio4, nho3 or HC1. 22. The anodized diamond-coated electrode according to item 20 of the application, wherein the alkaline solution contains KOH or NaOH. 2 3. A uric acid sensor using anodized diamond-coated electrodes, including: a cell body; a cavity formed in the cell body for receiving a test solution; a diamond-coated electrode that has undergone anodization, used as an active electrode ; And the reference electrode and the counter electrode, immersed in the test solution in the cavity, maintaining a constant distance from the diamond-coated electrode. 2 4. A uric acid analysis system, comprising: a uric acid sensor including a diamond-coated electrode that has undergone anodizing, and a reference electrode and a counter electrode as active electrodes in its cavity; and 528867 A control / detection section, which feeds a test solution into the cavity of the sensor, and controls / detects signals generated by the anodized diamond-coated electrode, the reference electrode, and the counter electrode; and an analysis device for receiving control by the detection section / Detected signal to analyze the substance in question. 25. A flow cell-based uric acid analysis system including an anodized diamond-coated electrode used as an active electrode; a flow cell including an active electrode, a reference electrode, and a counter electrode in its cavity; signal control / detection Part, so the signals generated by the anodized diamond-coated electrode, and the reference electrode and the counter electrode can be controlled / detected; an analysis device for receiving the signals controlled / detected by the detection part for analysis; and a flow injection device, including: Background solution tank for storing background solution; pump for driving background solution; solution guide with injection valve for continuous injection of sample into flow cell under pump pressure; and for flow cell after each measurement An outlet for the contents, where the sample is continuously fed into the flow cell along with the background solution through the solution guide to continuously analyze the substance in question. 52886JZI Supplement Liao J η Gull Figure 30 一 ·· __, wj ·.-., Yu ·, 52886¾. 〇.ί0 Figure 31Α Figure 31C 5288 ^ 67 ... 9L9. | § 34 Injection group 胲 Search Η Figure 35A Figure 35B