KR102133667B1 - Sensitive detecting method for detergent component etidronic acid utilizing phase transformation of copper compound - Google Patents

Abstract

The present invention relates to a method of detecting a trace of etidronic acid, which is a detergent component, utilizing phase transformation of a copper compound, capable of easily detecting etidronic acid using a change in color occurring when copper hydroxide is transformed into copper oxide through a colorimetric method using a metal coordination compound and capable of easily determining existence of the etidronic acid by observing a clear change in color even when only 1 ppm or more of the etidronic acid exists. The method of the present invention is advantageous in that an organic solvent is not used in the method, and thus, a testing method is not harmful, and the etidronic acid can be detected at significantly lower costs compared to a conventional method even without using expensive test chemicals.

Description

{Sensitive detecting method for detergent component etidronic acid utilizing phase transformation of copper compound}

The present invention relates to a method for detecting trace amounts of etidronic acid which is a detergent component using a phase transition of a copper compound.

The cleaning agent is the most frequently used hygiene product among daily hygiene products, and is widely used from vegetables/fruits to cleaning of cooking utensils. The cleaning agents are divided into three types according to their use, and the first type cleaning agent is used to wash vegetables/fruits that can be eaten by humans, and the second type cleaning agent is food including automatic dishwashers such as processing equipment and cooking utensils. It is used to wash utensils/containers, and three kinds of cleaning agents are used to wash utensils for manufacturing/processing such as food production equipment and processing equipment.

When using a class 1 detergent, do not immerse the vegetables or fruits in the detergent solution for more than 5 minutes, and after washing the vegetables, fruits, food or cooking utensils with the class 1 detergent, be sure to wash with water suitable for drinking. At this time, when using flowing water, wash vegetables or fruits for more than 30 seconds, and dishware for 5 seconds or more. When using non-flowing water, exchange water and wash it more than 2 times. After using two or three types of detergent, wash with water suitable for drinking so that no detergent remains on the food or cooking utensils, and be careful not to use other than intended use or use more than the prescribed amount.

However, because these cleaning methods are not well adhered to by regulations, or due to carelessness in cleaning, strong residual function of the cleaning agent ingredients, residual cleaning agent ingredients remain in vegetables, fruits, cooking utensils, etc., and these ingredients enter the body and act as toxic ingredients. In addition, it causes skin diseases such as atopy and allergies, and acts as an environmental hormone to induce premature ejaculation, causing various problems such as disturbing the endocrine system.

Etidronic acid can be used as a drug in the treatment of Paget's disease. However, when administered to children, there is a possibility of affecting bone growth, and there are reports of rickets symptoms caused by long-term administration of 10 to 20 mg/Kg/day in children. Therefore, safety and effectiveness for children are not established, so do not administer to children. On the other hand, a wide variety of components are present in the cleaning agent, the content also appears to have a large variation, and certain components may be easily washed down during the washing process, making it difficult to detect, and it is also analyzed that it is difficult to analyze with a simple detection kit. Considering these points, the ease of analysis and versatility of components in the cleaning agent are taken into consideration, and the residual amount of etidronic acid (etidronic acid or 1-hydroxyethane-1,1-diphosphonic acid/HEDP) contained in the alkaline detergent is checked. What can be done can be considered as an indicator that the cleaner has been well removed from vegetables, fruits, and cookware.

As a method for detecting etironic acid, a method of detecting phosphate can be used. In the conventional method for detecting phosphate, ammonium, a molybdate produced by the reaction of phosphate ion with ammonium molybdate, is reduced to stannous chloride. It was a method of visually identifying the color of the molybdenum blue water produced by the naked eye (the Molybdenum Blue Colorimetric Method according to the Food Ingredients Test Method in the General Test Methods of the Food and Drug Administration). However, this method has a problem in that it is expensive because it uses ammonium molybdenum and stannous chloride. However, even if the analysis is carried out at such a high cost, the method of detecting ethonic acid is not clearly identified as a method for detecting phosphate because it does not exist in the form of phosphate because it is not easily deprotonated due to the large molecule of etidronic acid. Became.

Accordingly, the present inventors have completed the present invention by developing a method for detecting the presence or absence of etidronic acid remaining in fruits, vegetables, and various dishes by preparing a reagent that reacts with the etidronic acid component to cause a color reaction. .

Republic of Korea Registered Patent No. 10-1503638 (Invention name: Method and detection kit for the detection of harmful disinfectant components in living environment products, Applicant: Yeungnam University Industry-University Cooperation Foundation, Registration Date: March 11, 2015) Republic of Korea Registered Patent No. 10-1340766 (Invention name: High concentration of phosphate phosphorus detection reagent and detection kit, Applicant: Seoul National University Industry-University Cooperation Foundation registration date: December 05, 2013) Republic of Korea Registered Patent No. 10-1350081 (Invention name: High concentration of phosphate phosphorus concentration detection method, Applicant: Seoul National University Industry-University Cooperation Foundation registration date: January 03, 2014)

Yannick Cudennec, Andre Lecerf, The transformation of Cu(OH) into CuO, Solid State Sciences, 2003, 5(11), 1471-1474.

Yannick Cudennec, Andre Lecerf, The transformation of Cu(OH) into CuO, Solid State Sciences, 2003, 5(11), 1471-1474.

An object of the present invention is to provide a method for detecting trace amounts of etidronic acid, which is a detergent component using a phase transition of a copper compound.

(First step) preparing an aqueous solution of copper(II) chloride and an aqueous sodium hydroxide solution;

(Second step) preparing a mixed solution of an aqueous solution of copper chloride and an aqueous sodium hydroxide solution;

(3rd step) adding a washing solution to check the residual state of water and etidronic acid, respectively, to the mixed solution; And,

(4th step) After mixing the mixed solution to which the water and the washing solution are added, leaving them in a standing state to compare the color change of the mixed solution in which the water and the washing solution are mixed; a cleaning agent component using a phase transition of a copper compound containing The present invention relates to a method for detecting trace amounts of phosphoric acid.

The concentration of the aqueous solution of cupric chloride in the first step is preferably 8000 to 12000 ppm, and the concentration of the aqueous sodium hydroxide solution is 0.8 to 1.2 M. At this time, when the concentration of the aqueous solution of copper chloride is less than 8000 ppm or more than 12000 ppm, or the concentration of the aqueous sodium hydroxide solution is less than 0.8M or more than 1.2M, the detection of etidronic acid may not be performed well. .

In the second step, based on 10 ml aqueous solution of copper chloride, 1.5-2.5 ml of sodium hydroxide aqueous solution may be mixed to prepare a mixed solution. In this process, even if less than 1.5 ml of sodium hydroxide aqueous solution is mixed or more than 2.5 ml based on 10 ml of aqueous solution of cupric chloride, the detection of etidronic acid may also be difficult.

In the third step, the mixed solution to which water is added is a control group, and the mixed solution to which the washing solution to check the residual state of etidronic acid is added is prepared as a test group.

It is preferable to mix at least 15 ml or more of the washing solution to check the residual state of water and etidronic acid in the mixed solution prepared in the third step. If the volume to which the washing solution is added is 15 ml or more, it is not a problem to suppress the color change of the mixed solution, but it is good to mix up to 25 ml within a suitable time or for proper reaction with the mixed solution.

In addition, a standard sample group in which the standard solution of etidronic acid is added to the mixed solution in the third step may be prepared. Therefore, in order to prepare the standard sample group in the third step, when adding the standard solution of etidronic acid, preferably, the standard solution of etidronic acid may be added in the same volume as the detergent solution. That is, at least 15 ml of the standard solution of etidronic acid (aqueous solution) may be mixed. The standard solution of etidronic acid is suitable for use as a standard solution even if it is not at a high concentration, and is suitable for use as a standard solution even if it is at least 1 ppm or more and within 10 ppm.

In the third step, the washing solution is characterized in that it is a washing solution of fruits, vegetables or dishes, and more preferably, the washing solution containing etidronic acid is used to confirm the etidronic acid remaining on the surface of the washed fruits, vegetables or dishes. To this end, it may be a washing solution obtained by further washing the fruits, vegetables, or dishes that have been washed. That is, it is possible to easily detect the etidronic acid remaining on the surface of the fruit, vegetable or tableware in which the cleaning agent is used by obtaining the detection solution in this easy manner.

In the fourth step, after mixing the mixed solution to which water and the washing solution are added, it is left at least for 2 hours or more, and if the color change does not progress until 3 hours, it is assumed that etridonic acid is not detected.

Accordingly, the present invention provides a kit for detecting etidronic acid using the above method.

In yet another aspect, the present invention can provide a kit for detecting etidronic acid, comprising an aqueous solution of Copper(II) chloride and an aqueous sodium hydroxide solution.

As described above, the trace detection method of ethironic acid, which is a detergent component using the phase transition of the copper compound of the present invention, has a blue colloidal copper(II) chloride dihydrate when the aqueous solution of copper(II) chloride dihydrate and sodium hydroxide are mixed. As a result of the phenomenon that it turns black as it passes, the blackened material is a form in which copper hydroxide is converted to copper oxide through phase transition. In the presence of etidronic acid, phase transition occurs from etidronic acid to copper oxide from copper hydroxide. It is using the principle of inhibiting things.

Therefore, in the present invention, it is possible to check the presence or absence of etidronic acid at a concentration of 1 ppm by comparing color development between the group added based on distilled water and the group added with etidonic acid instead of distilled water.

The present invention relates to a method for detecting trace amounts of etidronic acid, which is a detergent component using a copper compound, and it is easy to detect etidronic acid using a color change occurring in the process of copper hydroxide being converted to copper oxide through a colorimetric method using a metal coordination compound. On the other hand, it is possible to easily determine the presence or absence of etidronic acid by observing a clear color change even if only 1 ppm or more of etidronic acid is present. The method of the present invention has an advantage in that it is possible to detect etidronic acid at a significantly lower cost than the existing method without using an expensive test chemical, even though the test method is not harmful because no organic solvent is used.

Figure 1 is a copper (II) chloride aqueous solution (10,000 ppm) and sodium hydroxide aqueous solution (1.0 M) mixed solution of ethitronic acid is added to each concentration of 1, 2, 3, 5, 10 ppm concentration after the color change Shows the photos confirmed by time.

Hereinafter, examples will be described in detail to help understanding of the present invention. However, the following examples are merely illustrative of the contents of the present invention, and the scope of the present invention is not limited to the following examples. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

<Example 1. Detection of etidronic acid>

An aqueous copper(II) chloride solution (10,000 ppm), an aqueous sodium hydroxide solution (1.0 M), an aqueous solution of etidronic acid (1, 2, 3, 5, 10 ppm), distilled water, and a 45 mL conical tube were prepared.

After adding 10 mL of a copper(II) chloride dihydrate aqueous solution (10,000 ppm) to a 45 mL conical tube, 6 mixed solutions were prepared by adding 2 mL of sodium hydroxide aqueous solution. To the conical tube containing the mixed solution, 20 mL of the prepared aqueous solution of etidronic acid was added to each conical tube, and distilled water was added to the control group instead of the aqueous solution of etidronic acid. After mixing evenly for 10 seconds, each tube was allowed to stand, and photographs were taken every 30 minutes to observe the color change for a total of 2 hours. The observation results are shown in FIG. 1.

As a result, even if the aqueous solution of etidronic acid was 1 ppm, as shown in FIG. 1, the mixed solution added in trace amounts did not change color and still had a blue color peculiar to the copper aqueous solution, but the control solution containing no aqueous solution of etidronic acid (ethidonic acid) 0ppm) was changed to indigo color over time, and it was confirmed that the color change gradually became closer to black. This is because etidronic acid inhibited the phase transition of blue colloidal copper hydroxide to black copper oxide.

<Example 2. Confirmation of the appropriate concentration of the coloring reagent>

To confirm the appropriate concentrations of the aqueous solution of copper(II) chloride and sodium hydroxide, which are suitable for detecting etironic acid, the experiment was conducted in the same manner as in Example 1, but the concentration of each reagent was as follows in Table 1, and the concentration of 1 ppm was added. It was confirmed that the lactic acid was detectable (the mixing ratio of each reagent was the same).

Condition Copper(II) chloride aqueous solution
(10 ml) Sodium hydroxide aqueous solution
(2 ml) Detection Example 1 10000 ppm 1.0 M detection Example 2-1 10000 ppm 1.2 M detection Example 2-2 10000 ppm 0.8 M detection Example 2-3 8000 ppm 1.0 M detection Example 2-4 8000 ppm 1.2 M detection Example 2-5 8000 ppm 0.8 M detection Example 2-6 12000 ppm 1.0 M detection Example 2-7 12000 ppm 1.2 M detection Example 2-8 12000 ppm 0.8 M detection Example 2-9 10000 ppm 0.6 M Non-detection Example 2-10 10000 ppm 1.4 M Non-detection Example 2-11 8000 ppm 0.6 M Non-detection Example 2-12 8000 ppm 1.4 M Non-detection Example 2-13 12000 ppm 0.6 M Non-detection Example 2-14 12000 ppm 1.4 M Non-detection Example 2-15 14000 ppm 1.0 M Non-detection Example 2-16 6000 ppm 1.0 M Non-detection

Referring to the results in Table 1, the concentration of the aqueous copper(II) chloride solution suitable for detecting etidronic acid should be 8000 to 12000 ppm, and at the same time, it is confirmed that the concentration of the aqueous sodium hydroxide solution is 0.8 to 1.2 M. , If it is out of concentrations other than this, it is understood that the detection of low concentrations of etidronic acid, such as 1 ppm, was not performed well.

<Example 3. Confirmation of the appropriate mixing ratio of the coloring reagent>

The same procedure as in Example 1 was carried out to detect 1 ppm of etidronic acid, but the mixing ratios of copper(II) chloride aqueous solution (10,000 ppm), sodium hydroxide aqueous solution (1.0 M), and etidronic acid aqueous solution (1 ppm) were as follows. It was changed as shown in 2 (the concentration of each reagent was the same).

As a result, referring to Table 2, based on 10 ml of aqueous copper(II) chloride solution, 1.5 to 2.5 ml of sodium hydroxide aqueous solution should be mixed, and at least 15 ml of ethironic acid aqueous solution should be mixed to detect even a concentration of 1 ppm. Can be confirmed.

Condition Copper(II) chloride aqueous solution (10000 ppm) Sodium hydroxide aqueous solution (1.0 M) Etidronic acid
(1ppm) Detection Example 1 10 ml 2.0 ml 20 ml detection Example 3-1 10 ml 1.5 ml 20 ml detection Example 3-2 10 ml 2.5 ml 20 ml detection Example 3-3 10 ml 2.0 ml 15 ml detection Example 3-4 10 ml 2.0 ml 25 ml detection Example 3-5 10 ml 2.5 ml 25 ml detection Example 3-6 10 ml 1.5 ml 15 ml detection Example 3-7 10 ml 2.5 ml 15 ml detection Example 3-8 10 ml 1.5 ml 25 ml detection Example 3-9 10 ml 1.0 ml 20 ml Non-detection Example 3-10 10 ml 2.5 ml 20 ml Non-detection Example 3-11 10 ml 2.0 ml 10 ml Non-detection

When finally referring to the results of Examples 2 and 3, ethionic acid was added to a mixed solution in which 1.5 to 2.5 ml of a 0.8-1.2 M sodium hydroxide aqueous solution was mixed based on 10 ml of a copper(II) chloride aqueous solution of 8000 to 12000 ppm. It can be confirmed that at least 15 ml of the included solution was added to detect a low concentration of etidronic acid up to 1 ppm.

Claims (10)

delete delete delete delete (First step) preparing an aqueous solution of copper(II) chloride and an aqueous sodium hydroxide solution;
(Second step) preparing a mixed solution of an aqueous solution of copper chloride and an aqueous sodium hydroxide solution;
(3rd step) adding a washing solution to check the residual state of water and etidronic acid, respectively, to the mixed solution; And,
(4th step) comparing the color change of the mixed solution in which the water and the washing solution are mixed by mixing the mixed solution in which the water and the washing solution are added, and then left standing;
Method for detecting a trace amount of etidronic acid using a phase transition of a copper compound comprising a. The method of claim 5,
The concentration of the aqueous solution of cupric chloride in the first step is 8000 ~ 12000 ppm, characterized in that the trace amount detection method of etidronic acid using the phase transition of the copper compound. The method of claim 5,
The concentration of sodium hydroxide aqueous solution in the second step is 0.8 ~ 1.2 M, characterized in that the trace amount detection method of ethitronic acid using a phase transition of a copper compound. The method of claim 5,
A method of detecting trace amounts of etidronic acid using phase transition of a copper compound, wherein a standard sample group in which an aqueous solution of etidronic acid is added to the mixed solution is prepared in the third step. The method of claim 5,
In the third step, the washing solution is a washing solution of fruits, vegetables, or dishes. A method for detecting trace amounts of etidronic acid, which is a detergent component using a phase transition of a copper compound. delete

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