A rapid method for detecting illegal additives in gel-based health food products

Abstract

This invention discloses a rapid method for detecting illegal additives in gel-type health foods, comprising: S1, adding 2-hydroxypropionic acid solution to the gel-type health food, heating to dissolve the gel, then adding 4-methyl-2-pentanol solution, and extracting the supernatant to obtain the test solution containing the illegal additive; S2, performing SERS spectroscopy on the test solution. This method is simple, efficient, and highly sensitive, enabling rapid detection of illegal additives such as metformin, sibutramine, sildenafil, and glimepiride in gel-type health foods.

Description

Technical Field

[0001] This invention belongs to the field of health food testing, and in particular relates to a method for rapid detection of illegal additives in gel-type health foods. Background Technology

[0002] In recent years, as people have become increasingly aware of the importance of diet to human health, more and more people tend to choose foods with health benefits, such as those that lower blood sugar and blood lipids, and jellies that promote weight loss. However, in pursuit of profit and short-term effects, unscrupulous merchants illegally add chemical drugs to health foods. For example, biguanide hypoglycemic agents, mainly metformin hydrochloride and benzoyl hydrochloride, are frequently added to health products made into gels and capsules; sibutramine hydrochloride, which has the dual effects of suppressing appetite and enhancing metabolism, is often illegally added to weight-loss products, such as weight-loss jellies. Long-term, irrational consumption of these adulterated health products may lead to serious adverse drug reactions.

[0003] Currently, methods for detecting illegal additives mainly include thin-layer chromatography (TLC), high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), ultra-high performance liquid chromatography-mass spectrometry (UPLC-MS-MS), and gas chromatography-mass spectrometry (GC-MS). These methods can provide high-precision and reliable results, but almost all of them require cumbersome pretreatment and time-consuming procedures. Furthermore, these instruments are expensive, and the experimental conditions are very strict, making them difficult to operate and unsuitable for on-site detection. Compared to these methods, Raman spectroscopy has its own advantages. It can obtain the "fingerprint information" of target molecules and provide higher information content, and it can also analyze aqueous samples. Surface-enhanced Raman scattering (SERS) is a surface-sensitive technique that can enhance Raman spectroscopy by 10 times compared to normal Raman spectroscopy. 4 -10 6 The resonance enhancement factor can reach 10. 14 -10 15 It is not only simple and convenient, suitable for rapid on-site testing, but also has good reproducibility and stability.

[0004] Therefore, establishing a rapid, accurate, and efficient SERS detection method for illegal additives such as metformin and sibutramine in gel-type health foods is of great practical significance for strengthening the management of health care products. Summary of the Invention

[0005] Based on the above-mentioned technical problems, the present invention provides a method for the extraction and SERS detection of illegal additives in gel-type health foods. This method is simple, efficient and highly sensitive, and can achieve rapid detection of illegal additives such as metformin, sibutramine, sildenafil and glimepiride in gel-type health foods.

[0006] The specific solution of this invention is as follows:

[0007] This invention provides a method for rapid detection of illegal additives in gel-type health foods, comprising: S1, adding 2-hydroxypropionic acid solution to the gel-type health food, heating to dissolve the gel, then adding 4-methyl-2-pentanol solution, and extracting the supernatant to obtain the test solution containing the illegal additive; S2, performing SERS spectral detection on the test solution.

[0008] This invention addresses the characteristics of gel-type health foods that are insoluble and prone to repeated solidification. When preparing the test solution, 2-hydroxypropionic acid solution is combined with 4-methyl-2-pentanol. This ensures that illegal additives are dispersed in the test solution and avoids repeated solidification, greatly improving the accuracy of surface-enhanced Raman spectroscopy detection of illegal additives in gel-type health foods.

[0009] Preferably, in S1, the mass fraction of the 2-hydroxypropionic acid solution is 0.3-1.5%; the volume ratio of the 2-hydroxypropionic acid solution to the 4-methyl-2-pentanol solution is ≥3.

[0010] Preferably, in S1, the volume ratio of 2-hydroxypropionic acid solution to 4-methyl-2-pentanol solution is 3-8:1.

[0011] Preferably, in S1, the heating temperature is 90-100℃ and the heating time is 5-20min.

[0012] Preferably, in S2, the active substrate used for SERS detection includes ZnO nanosol.

[0013] Preferably, in S2, the active substrate used for SERS detection also includes a silicon wafer.

[0014] Preferably, in S2, the active substrate used for SERS detection is obtained by centrifuging ZnO nanosol, dropping it onto a silicon wafer, and then drying it.

[0015] This invention uses ZnO nanosol as the SERS substrate, which is low in cost, highly sensitive, and highly reproducible.

[0016] Preferably, the illegal additive is at least one of metformin, sibutramine, tadalafil, sildenafil, glimepiride, ephedrine, phenolphthalein, fluoxetine, furosemide, and fenfluramine.

[0017] The SERS spectrum obtained using the method described in this invention can be automatically identified and compared with SERS spectra in a standard spectral library, thus confirming the presence of illegal additives. This method can detect the aforementioned illegal additives simultaneously, and can also detect multiple illegal additives at the same time when their characteristic peaks do not overlap.

[0018] The beneficial effects of this invention are:

[0019] This invention provides a SERS detection method for illegal additives in gel-type health foods. Compared with liquid chromatography and gas chromatography, the SERS detection method of this invention for illegal additives such as metformin and sibutramine in gel-type health foods has simpler pretreatment, shorter detection time, and higher accuracy, and can be used for rapid on-site detection. Attached Figure Description

[0020] Figure 1 The SERS spectrum obtained in Example 1;

[0021] Figure 2 The SERS spectrum obtained in Example 2;

[0022] Figure 3 The SERS spectrum obtained in Example 3;

[0023] Figure 4 The SERS spectrum obtained in Comparative Example 1; Detailed Implementation

[0024] The technical solution of the present invention will be described in detail below through specific embodiments. However, it should be clearly stated that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0025] Example 1

[0026] A method for rapid detection of illegal additives in gel-based health food products includes the following steps:

[0027] S1. Place 20 mg of gel-type health food sample in a 2 mL centrifuge tube, add 300 μL of 0.5% 2-hydroxypropionic acid solution, heat at 90 °C for 10 min to dissolve it completely, add 100 μL of 4-methyl-2-pentanol solution, mix well, and extract the upper layer solution to obtain the test solution containing illegal additives.

[0028] S2. After centrifuging, ZnO nanosol is dropped onto a silicon wafer and dried to serve as a SERS active substrate. The test liquid obtained in S1 is added to the SERS active substrate, and a Raman spectrometer is used to vertically strike the SERS active substrate for SERS detection. The laser power of the Raman spectrometer is 200mW and the integration time is 5s. After the detection is completed, the SERS spectrum is obtained.

[0029] The SERS diagram obtained in this embodiment is as follows: Figure 1 As shown, after automatic identification and comparison with the standard spectral library, it was determined that the gel-type health food contained metformin, and the detection limit could reach 50 ppb.

[0030] Example 2

[0031] A method for rapid detection of illegal additives in gel-based health food products includes the following steps:

[0032] S1. Place 20 mg of gel-type health food sample in a 2 mL centrifuge tube, add 300 μL of 0.5% 2-hydroxypropionic acid solution, heat at 90℃ for 10 min to dissolve it completely, add 60 μL of 4-methyl-2-pentanol solution, mix well, and extract the upper layer solution to obtain the test solution containing illegal additives.

[0033] S2. After centrifuging, ZnO nanosol is dropped onto a silicon wafer and dried to serve as a SERS active substrate. The test liquid obtained in S1 is added to the SERS active substrate, and a Raman spectrometer is used to vertically strike the SERS active substrate for SERS detection. The laser power of the Raman spectrometer is 200mW and the integration time is 5s. After the detection is completed, the SERS spectrum is obtained.

[0034] The SERS diagram obtained in this embodiment is as follows: Figure 2 As shown, after automatic identification and comparison with the standard spectral library, it was determined that the gel-type health food contained sibutramine, and the detection limit could reach 100 ppb.

[0035] Example 3

[0036] A method for rapid detection of illegal additives in gel-based health food products includes the following steps:

[0037] S1. Place 20 mg of gel-type health food sample in a 2 mL centrifuge tube, add 300 μL of 0.5% 2-hydroxypropionic acid solution, heat at 90℃ for 10 min to dissolve it completely, add 50 μL of 4-methyl-2-pentanol solution, mix well, and extract the upper layer solution to obtain the test solution containing illegal additives.

[0038] S2. After centrifuging, ZnO nanosol is dropped onto a silicon wafer and dried to serve as a SERS active substrate. The test liquid obtained in S1 is added to the SERS active substrate, and a Raman spectrometer is used to vertically strike the SERS active substrate for SERS detection. The laser power of the Raman spectrometer is 200mW and the integration time is 5s. After the detection is completed, the SERS spectrum is obtained.

[0039] The SERS diagram obtained in this embodiment is as follows: Figure 3 As shown, after automatic identification and comparison with the standard spectral library, it was determined that the gel-type health food contained phenolphthalein, and the detection limit could reach 100 ppb.

[0040] Comparative Example 1

[0041] A method for rapid detection of illegal additives in gel-based health food products includes the following steps:

[0042] S1. Place 20 mg of gel-type health food sample in a 2 mL centrifuge tube, add 300 μL of cyclohexane, heat at 90 °C for 10 min to dissolve it completely, add 50 μL of 4-methyl-2-pentanol solution, mix well, and extract the upper layer solution to obtain the test solution.

[0043] S2. After centrifuging, ZnO nanosol is dropped onto a silicon wafer and dried to serve as a SERS active substrate. The test liquid obtained in S1 is added to the SERS active substrate, and a Raman spectrometer is used to vertically strike the SERS active substrate for SERS detection. The laser power of the Raman spectrometer is 200mW and the integration time is 5s. After the detection is completed, the SERS spectrum is obtained.

[0044] The gel-type health food sample used in this comparative example is the same as that in Example 1, both containing metformin. The SERS chromatogram obtained in this comparative example is shown below. Figure 4 As shown, automatic identification and comparison with the standard spectral library showed that metformin was not detected.

[0045] Comparative Example 2

[0046] Compared to Example 1, this comparative example only adjusted the volume ratio of 2-hydroxypropionic acid solution to 4-methyl-2-pentanol solution. It was found that when the volume ratio of 2-hydroxypropionic acid solution to 4-methyl-2-pentanol solution was less than 3:1, specifically 1:1, the mixed solution would solidify and could not be reconstituted, making subsequent operations impossible.

[0047] Comparative Example 3

[0048] Compared to Example 1, this comparative example only replaced the 2-hydroxypropionic acid solution with a hydrochloric acid solution, while keeping all other conditions unchanged. The gel dissolved, but the dissolved solution damaged the SERS-enhanced substrate, causing the substrate to carbonize and break down, making it impossible to detect.

[0049] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for rapid detection of illegal additives in gel-based health food products, characterized in that, include: S1. Add 2-hydroxypropionic acid solution to gel-type health food, heat to dissolve the gel, then add 4-methyl-2-pentanol solution, extract the upper layer liquid, and obtain the test solution containing illegal additives; S2. After centrifuging, ZnO nanosol is dropped onto a silicon wafer and dried to serve as a SERS active substrate. The test solution obtained in S1 is added to the SERS active substrate, and SERS is detected using a Raman spectrometer with a laser power of 200mW and an integration time of 5s. In S1, the mass fraction of 2-hydroxypropionic acid solution is 0.3-1.5%; the volume ratio of 2-hydroxypropionic acid solution to 4-methyl-2-pentanol solution is ≥3; The illegal additives are at least one of metformin, sibutramine, tadalafil, sildenafil, glimepiride, ephedrine, phenolphthalein, fluoxetine, furosemide, and fenfluramine.

2. The method for rapid detection of illegal additives in gel-type health foods according to claim 1, characterized in that, In S1, the volume ratio of 2-hydroxypropionic acid solution to 4-methyl-2-pentanol solution is 3-8:

1.

3. The method for rapid detection of illegal additives in gel-type health foods according to claim 1 or 2, characterized in that, In S1, the heating temperature is 90-100℃ and the heating time is 5-20min.

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