阅读说明：本技术 一种硼酸和/或硼酸盐的检测方法 (Detection method of boric acid and/or borate ) 是由 吴震 于 2021-03-01 设计创作，主要内容包括：本发明公开了一种硼酸和/或硼酸盐的检测方法,包括如下步骤：将无水酸溶于无水质子化溶剂1中,形成试剂A；将姜黄素溶于无水质子化溶剂2中,然后浸入滤纸,取出干燥得到姜黄试纸；将待测样品与试剂A混合得到混合物,将所述混合物滴加到所述姜黄试纸上,根据姜黄试纸的颜色变化以对硼酸和/或硼酸盐进行定性检测。本发明的检测方法操作简单方便,显色过程不需要加热或干燥等操作,用时短,结果易于判断,特征性良好,不需要其他设备和条件,适合现场操作,满足监督部门、检测机构和个人等现场快速检测的需求。(The invention discloses a method for detecting boric acid and/or borate, which comprises the following steps: dissolving anhydrous acid in an anhydrous protonation solvent 1 to form a reagent A; dissolving curcumin in an anhydrous protonation solvent 2, then immersing the curcumin in filter paper, taking out and drying to obtain turmeric test paper; mixing a sample to be detected with a reagent A to obtain a mixture, dripping the mixture onto the turmeric test paper, and carrying out qualitative detection on boric acid and/or borate according to the color change of the turmeric test paper. The detection method provided by the invention is simple and convenient to operate, does not need heating or drying and other operations in the color development process, is short in time consumption, easy to judge the result, good in characteristics, free of other equipment and conditions, suitable for field operation, and capable of meeting the requirements of field rapid detection of supervision departments, detection mechanisms, individuals and the like.)

1. A method for detecting boric acid and/or a borate, characterized by: the method comprises the following steps:

dissolving anhydrous acid in an anhydrous protonation solvent 1 to form a reagent A;

dissolving curcumin in an anhydrous protonation solvent 2, then immersing the curcumin in filter paper, taking out and drying to obtain turmeric test paper; mixing a sample to be detected with the reagent A to obtain a mixture, dripping the mixture onto the turmeric test paper, and carrying out qualitative detection on boric acid and/or borate according to the color change of the turmeric test paper.

2. The detection method according to claim 1, characterized in that: the anhydrous acid is anhydrous hydrogen chloride.

3. The detection method according to claim 1, characterized in that: the anhydrous protonated solvent 1 and the anhydrous protonated solvent 2 are independently anhydrous alcoholic solvents.

4. The detection method according to claim 3, characterized in that: the anhydrous protonated solvent 1 and the anhydrous protonated solvent 2 independently comprise at least one of anhydrous methanol and anhydrous ethanol.

5. The detection method according to claim 2, characterized in that: the mass ratio of the anhydrous hydrogen chloride to the anhydrous protonized solvent 1 is 0.1-30: 100.

6. the detection method according to claim 1, characterized in that: the dosage ratio of the sample to be detected to the reagent A is 10-100 mg: 0.05-0.5 mL.

7. The detection method according to claim 1, characterized in that: the sample to be detected is an anhydrous sample.

8. The detection method according to claim 7, characterized in that: the sample to be detected is an anhydrous solid powder sample.

9. The detection method according to claim 8, characterized in that: the sample to be detected is anhydrous solid powder cosmetics.

10. The detection method according to any one of claims 1 to 9, characterized in that: the qualitative detection of the boric acid and/or the borate according to the color change of the turmeric test paper is specifically that if the turmeric test paper is red, the boric acid and/or the borate in the sample to be detected is judged to be contained, and the deeper the red is, the higher the content of the boric acid and/or the borate in the sample to be detected is.

Technical Field

The invention relates to the technical field of chemical analysis, in particular to a detection method of boric acid and/or borate.

Background

Boric acid of formula H₃BO₃White powdery crystals or triclinic scaly gloss crystals; borate is a generic term for salts related to diboron trioxide and is often referred to simply as the orthoboric acid salt, with more commonly used borates including sodium tetraborate, commonly referred to as borax. Boric acid and borates are commonly used as external bactericides, disinfectants, astringents and preservatives, in cosmetics as antiseptic bacteriostats, and in products such as toilet powders and the like.

Boric acid and borate salts can cause acute poisoning, mainly manifested as gastrointestinal symptoms, such as nausea, vomiting, abdominal pain, diarrhea, etc., followed by dehydration, shock, coma or acute renal failure, with high fever, liver and kidney damage and convulsion, and in severe cases, death. Boric acid and borate are easily absorbed by injured skin to cause poisoning, resulting in poisoning reactions such as nausea, diarrhea, spasm, erythema, cyanosis, circulatory organ weakness, and nerve disorder. Boric acid and borates can cause chronic poisoning: when absorbed in small amounts from the gastrointestinal tract or skin over a long period, mild digestive symptoms, dermatitis, alopecia and liver and kidney damage may occur.

The technical specification for cosmetic safety (2015 edition) states that boric acid and borate are prohibited from being used in cosmetics for children under three years old, and there are label precautions and other requirements.

The cosmetic safety technical specification stipulates an azomethine-H spectrophotometric detection method of cosmetic boric acid and borate, and the method is complicated to use, long in test time, short in reagent shelf life and not suitable for rapid and on-site detection requirements. The detection methods of boric acid and borate include a micro-crystallization method, a color development method, a titration method, a spectrophotometry method, a fluorescence method, a liquid chromatography method, an atomic absorption spectrophotometry method, an optical rotation method, an inductively coupled plasma atomic emission spectrometry method, an inductively coupled plasma mass spectrometry method and the like. The method for detecting the boron element by using reagents such as curcumin, oxalic acid and the like is firstly applied to the field of agriculture, and then is continuously improved, the method for detecting the boric acid and the borate is widely applied to the fields of food, soil, cosmetics and the like by dissolving the treated boron in an aqueous solution, reacting with curcumin, oxalic acid, sulfuric acid and the like, heating, drying and developing color and the like. The curcumin color development method is simple and convenient to operate, good in sensitivity and characteristic, and suitable for quick screening of boric acid and borate, but has the problems of complicated sample pretreatment, heating and drying in the process and the like, and further has a space for improving the quick screening method of boric acid or borate in solid cosmetics.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a detection method of boric acid and/or borate, which can be used for rapidly and qualitatively detecting the boric acid and/or borate and is simple to operate.

The technical scheme adopted by the invention is as follows:

a method for detecting boric acid and/or borate comprises the following steps:

dissolving anhydrous acid in an anhydrous protonation solvent 1 to form a reagent A;

dissolving curcumin in an anhydrous protonation solvent 2, then immersing the curcumin in filter paper, taking out and drying to obtain turmeric test paper;

mixing a sample to be detected with the reagent A to obtain a mixture, dripping the mixture onto the turmeric test paper, and carrying out qualitative detection on boric acid and/or borate according to the color change of the turmeric test paper.

The detection method of boric acid and borate according to the invention at least comprises the following beneficial effects:

the invention utilizes the color reaction of complexing boric acid (boric acid can be formed by borate under the acidic condition) and protonated curcumin to generate red rose cyanine glycoside to carry out rapid qualitative detection on the boric acid and the borate. The detection method of the related art is generally carried out in an aqueous environment, curcumin is dissolved in an aqueous protonation solvent, then turmeric test paper is prepared, and an aqueous acid solution is added for detection. The inventor finds that the protonation of curcumin is greatly influenced by the water condition, so that the test paper needs to be heated and dried after the sample to be detected is dripped by adopting the method to enable red color to be displayed, the operation is complex, a factory is complex, the protonated curcumin has thermal instability, and the heating and drying influence the detection accuracy. Therefore, the detection method is carried out under the anhydrous condition, which is not only beneficial to the protonation of the curcumin, but also does not need heating and drying, improves the stability of the protonated curcumin, can immediately develop color when a mixture obtained by mixing a sample to be detected and the reagent A is dripped on the turmeric test paper, does not need waiting, and can quickly and accurately carry out qualitative detection on the boric acid and the borate.

In some embodiments of the invention, the anhydrous acid is anhydrous hydrogen chloride.

The acidic environment favors the complexation of boric acid with protonated curcumin, but not all acidic environments can be used in the detection methods of the present invention. For example, the presence of oxalic acid can lead to insufficient stability and sensitivity of the product, and sulfuric acid has oxidizing property and dehydration property and is not suitable for being applied on test paper; the acid strength of the phosphoric acid is not enough and can influence the judgment of the color development of the curcumin test paper.

In some embodiments of the present invention, the anhydrous protonated solvent 1 and the anhydrous protonated solvent 2 are independently anhydrous alcohol solvents, independently comprising at least one of anhydrous methanol and anhydrous ethanol, and the anhydrous protonated solvent 1 and the anhydrous protonated solvent 2 may be the same or different.

The detection method requires that the used anhydrous protonized solvent can dissolve anhydrous hydrogen chloride and boric acid and borate, so that color reaction can be normally carried out; the anhydrous protonized solvent is required to be liquid at normal temperature and has normal-temperature volatility, so that the color reaction is more sensitive and the color judgment is not influenced, and the anhydrous alcohol solvents such as anhydrous methanol, anhydrous ethanol and the like which are preferred by the method are suitable. In addition, the color change product rose cyanine glycoside generated in the detection process can be dissolved in an alcohol solvent and can not be dissolved in water or an aprotic solvent, so that the detection sensitivity can be improved by selecting an anhydrous alcohol solvent.

In some embodiments of the invention, the mass ratio of the anhydrous hydrogen chloride to the anhydrous protonated solvent 1 is from 0.1 to 30: 100.

in some embodiments of the present invention, the drying method in the turmeric test paper obtained by drying is natural drying.

In some embodiments of the present invention, the ratio of the sample to be tested to the reagent a is 10-100 mg: 0.05-0.5 mL. Generally, the volume of 1 drop of liquid is about 0.05mL, and in actual operation, the detection can be performed according to the proportion of dripping 1-10 drops of the reagent A into 10-100 mg of a sample to be detected.

In some embodiments of the present invention, the sample to be tested is an anhydrous sample, preferably an anhydrous solid powder sample. The detection method can directly detect the solid sample without any pretreatment on the sample to be detected, thereby simplifying the operation and saving the detection time. Meanwhile, the reagent A and the turmeric test paper are not hydrated, and a water-free sample to be detected and protonated curcumin rapidly undergo color reaction under the condition of an anhydrous solvent, so that the detection sensitivity is improved, the heating and drying process is omitted, and the detection speed is increased.

In some embodiments of the present invention, the sample to be tested is an anhydrous solid powder cosmetic.

In some embodiments of the present invention, the qualitative detection of boric acid and/or borate according to the color change of the turmeric test paper is specifically that if the turmeric test paper shows red color, it is determined that the sample to be detected contains boric acid and/or borate, and the deeper the red color is, the higher the content of boric acid and/or borate in the sample to be detected is.

In some embodiments of the invention, the detection method further comprises the steps of: dripping a mixture obtained by mixing the sample to be detected and the reagent A on turmeric test paper, dripping the reagent A on turmeric test paper as a blank, and comparing the test paper in which the mixture is dripped with the blank; if the test paper added with the mixture appears red compared with the blank, judging that the sample to be detected contains boric acid and/or borate; and if the test paper added with the mixture does not appear red compared with the blank, judging that the sample to be detected does not contain boric acid and borate.

In some embodiments of the present invention, after a mixture obtained by mixing the sample to be tested and the reagent a is dropped on the turmeric test paper, the comparison and determination can be performed after waiting for 0-5 min, and generally, the mixture can be immediately developed after being dropped on the turmeric test paper, and the determination can be performed without waiting.

Compared with the prior art, the invention has the following beneficial effects:

the detection method disclosed by the invention is simple and convenient to operate, does not need heating or drying and other operations, is short in time consumption, easy to judge the result, good in characteristics, does not need other equipment and conditions, is suitable for field operation, and meets the requirements of field rapid detection of supervision departments, detection mechanisms, individuals and the like.

Drawings

FIG. 1 is a schematic diagram of the detection process (A) and the detection results (B) of embodiments 1 to 3 of the present invention.

Detailed Description

The technical solution of the present invention will be further described below in detail with reference to specific examples.

Taking a solid powdery cosmetic which does not contain boric acid or borate as a negative sample (the solid powdery cosmetic is sampled by national cosmetic supervision and determined to contain no boric acid or borate by examination of legal methods); adding anhydrous boric acid into the negative sample, and mixing to prepare a boric acid sample with the boric acid mass concentration of 1mg/g or 10 mg/g; and adding sodium tetraborate into the negative sample, and mixing to prepare a borate sample with the reduced boric acid mass concentration of 10 mg/g.

Example 1

5g of dry hydrogen chloride is dissolved in 100g of anhydrous methanol to obtain a reagent A with the mass concentration of 5%.

A20 mg sample of boric acid (1 mg/g) was added to the tube, 2 drops of reagent A were added dropwise, and the mixture was shaken. The mixture was pipetted 1 drop-wise onto one end of the turmeric paper, while 1 drop of reagent a was added drop-wise onto the other end of the turmeric paper as a blank. The turmeric paper immediately after the addition of the mixture showed the results shown in figure 1.

As can be seen from FIG. 1, the turmeric test paper shows no red color after the reagent A is dripped, but the turmeric test paper shows light red color immediately after the mixture is dripped, which indicates that the detection method can be used for rapidly detecting boric acid and judging whether the sample to be detected contains boric acid.

Example 2

2g of dry hydrogen chloride is dissolved in 100g of absolute ethyl alcohol to obtain a reagent A with the mass concentration of 2%.

A boric acid sample (40 mg, 10 mg/g) was put into a test tube, 3 drops of the reagent A were added dropwise, and the mixture was shaken. The mixture was pipetted 1 drop-wise onto one end of the turmeric paper, while 1 drop of reagent a was added drop-wise onto the other end of the turmeric paper as a blank. The turmeric paper immediately after the addition of the mixture showed the results shown in figure 1.

As can be seen from FIG. 1, the test strips showed no red color after the addition of reagent A, while the test strips showed red color immediately after the addition of the mixture. Meanwhile, compared with the embodiment 1, the deepening of the red color of the embodiment is related to the concentration of the boric acid, which reflects that the detection method of the invention can rapidly compare the concentration of the boric acid in different samples to be detected according to the depth of the red color, and the deeper the red color is, the higher the concentration of the boric acid is.

Example 3

13g of dry hydrogen chloride is dissolved in 100g of anhydrous methanol to obtain a reagent A with the mass concentration of 13%.

80mg of the negative sample was placed in a test tube, 8 drops of reagent A were added dropwise, and the mixture was shaken. The mixture was pipetted 1 drop-wise onto one end of the turmeric paper, while 1 drop of reagent a was added drop-wise onto the other end of the turmeric paper as a blank. The results shown in FIG. 1 were obtained immediately after the addition of the mixture to the test strips (example 3-1 in FIG. 1).

Separately, 80mg of a 10mg/g borate sample was put into a test tube, 8 drops of reagent A were added dropwise, and the mixture was shaken. The mixture was pipetted 1 drop-wise onto one end of the turmeric paper, while 1 drop of reagent a was added drop-wise onto the other end of the turmeric paper as a blank. The results shown in FIG. 1 were obtained immediately after the addition of the mixture to the test strips (example 3-2 in FIG. 1).

As can be seen from fig. 1, after the negative sample is added dropwise, the turmeric test paper does not show any red color like the blank, and after the borate sample is added dropwise, the turmeric test paper immediately shows red color, which indicates that the detection method can be used for rapidly detecting borate and judging whether the sample to be detected contains borate.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.