CN114487203A - Method for detecting aristolochic acid in houttuynia cordata based on metal organic framework material dispersion solid-phase extraction combined with high performance liquid chromatography - Google Patents
Method for detecting aristolochic acid in houttuynia cordata based on metal organic framework material dispersion solid-phase extraction combined with high performance liquid chromatography Download PDFInfo
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Abstract
The invention discloses a method for detecting aristolochic acid compounds in houttuynia cordata based on metal organic framework material dispersion solid-phase extraction combined with high performance liquid chromatography. Belongs to the technical field of functional material preparation and endogenous harmful substance analysis. The method is based on metal organic framework material MIL-101(Fe), adopts a Dispersed Solid Phase Extraction (DSPE) method, combines a high performance liquid chromatography-diode array analysis technology (HPLC-DAD), can quickly and sensitively detect aristolochic acid I (AA-I) and aristolochic acid II (AA-II) in the houttuynia cordata, has instrument detection limits of 0.007 mg/L and 0.014 mg/L respectively, and provides a technical means for safety evaluation of the houttuynia cordata medicinal material.
Description
Technical Field
The invention relates to a method for detecting aristolochic acid compounds in houttuynia cordata based on metal organic framework material dispersion solid-phase extraction combined with high performance liquid chromatography, belonging to the technical field of functional material preparation and endogenous harmful substance analysis.
Background
In China, the eating history of the houttuynia cordata is recorded since east Han. The houttuynia cordata is also a herbal medicine recorded in Chinese pharmacopoeia, and has the effects of resisting bacteria and viruses, improving the immunity of the organism, promoting urination and the like. In recent years, rapid development of economy, traffic and media has driven increasingly widespread and deep culture and dietary communication, and cordate houttuynia, which is originally popular only in southwest areas, has begun to be widely popularized across the country. In daily diet, the tender stem part of the houttuynia cordata is used as a dish, or the whole plant of the houttuynia cordata is dried and then soaked in tea, and the medicinal use is to take the dried overground part or the fresh whole plant. Thus, houttuynia cordata is typically used as a plant for both food and medicine, and the whole plant is increasingly ingested.
Research finds that the houttuynia cordata probably contains aristolochic acid substances, and the aristolochic acid is a nitrophenanthrene carboxylic acid compound, has a very strong mutation-causing effect, can induce renal toxicity and can also be an important reason causing liver cancer, and is classified as a first carcinogen by international cancer research organization of world health organization. Among them, aristolochic acid I and aristolochic acid II have the strongest toxicity. In the 'Chinese pharmacopoeia' of 2020 edition, a method for measuring aristolochic acid in houttuynia cordata has not been specified yet. Therefore, the establishment of an accurate, reliable and sensitive detection system for aristolochic acid I (AA-I) and aristolochic acid II (AA-II) in houttuynia cordata is necessary for the safety evaluation of houttuynia cordata.
Disclosure of Invention
The invention aims to provide a rapid, simple and sensitive high performance liquid chromatography method for simultaneously detecting aristolochic acid compounds (aristolochic acid I and aristolochic acid II) in houttuynia cordata.
The technical scheme of the invention is as follows: an analytical method for simultaneously detecting 2 aristolochic acid compounds (aristolochic acid I and aristolochic acid II) in herba Houttuyniae based on dispersed solid phase extraction of metal organic framework material and high performance liquid chromatography-diode array technology is provided. 2 aristolochic acid compounds (aristolochic acid I and aristolochic acid II) in the houttuynia cordata are ultrasonically extracted by methanol, the aristolochic acid compounds are dispersed and solid-phase extracted by a metal organic framework material (MIL-101(Fe)), then the aristolochic acid compounds are eluted by an acetone solution containing 0.1-1.0% (v/v) glacial acetic acid, the eluent is rotated and evaporated to dryness, the methanol is redissolved, and the HPLC-DAD is adopted for detection.
The invention mainly comprises the following steps: preparing a metal organic framework material MIL-101 (Fe); liquid chromatography conditions; simultaneously detecting aristolochic acid I (AA-I) and aristolochic acid II (AA-II); pretreating a sample; and (4) detecting the sample.
A method for detecting aristolochic acid in houttuynia cordata based on a metal organic framework material MIL-101(Fe) by adopting a dispersive solid-phase extraction method and combining a high performance liquid chromatography technology is characterized by mainly comprising the following steps:
(1) preparation of Metal organic framework Material MIL-101(Fe)
Weighing 0.622-1.106 g terephthalic acid (H)2BDC) is dispersed in 40-70 mL of N, N-Dimethylformamide (DMF), stirred for 10-30 min, and added with 2.026-3.244 g of ferric chloride hexahydrate (FeCl)3·6H2O), continuously stirring for 30-60 min, then transferring the solution into a 100 mL polytetrafluoroethylene autoclave, and heating for 10-24 h at 110-130 ℃. Centrifuging at 8000-12000 rpm for 10min, discarding supernatant, washing the product with DMF and methanol in sequence, and vacuum drying at 60-70 ℃ for 12h to obtain the product.
(2) Conditions of liquid chromatography
A chromatographic column: a C18 column (4.6 mm. times.250 mm. times.5 μm); column temperature: 25 ℃; sample introduction volume: 10 mu L of the solution; mobile phase: acetonitrile-0.1% aqueous acetic acid (60: 40, v/v); flow rate: 1 mL/min; detection wavelength: 254 nm.
(3) Simultaneous detection of aristolochic acid I (AA-I) and aristolochic acid II (AA-II)
Preparing a series of AA-I and AA-II mixed standard solutions with mass concentration by using methanol as a solvent, measuring under the condition of the liquid chromatography, performing linear regression on the mass concentration X by using the peak area Y of each component, and ensuring that the linear relation between AA-I and AA-II is good (R is within the range of 0.05-20 mg/L) (R is2Not less than 0.9999), the detection Limit (LOD) is 0.007 mg/L and 0.014 mg/L respectively, and the quantification Limit (LOQ) is 0.024 mg/L and 0.045 mg/L respectively.
(4) Sample pretreatment
Crushing a dried houttuynia cordata sample, sieving the crushed houttuynia cordata sample by a sieve of 80-100 meshes, weighing 0.5 g (accurate to 0.001 g) of houttuynia cordata powder sample, adding 10 mL of methanol, carrying out ultrasonic treatment for 30 min, centrifuging the crushed houttuynia cordata sample at 6000-10000 rpm for 10min, taking supernatant, dispersing 20-100 mg of MIL-101(Fe) in 1 mL of supernatant, carrying out vortex oscillation for 10-40 min, centrifuging the supernatant at 8000-12000 rpm for 10min, discarding the supernatant, adding 3-10 mL of acetone containing 0.1-1.0% (v/v) of glacial acetic acid, carrying out ultrasonic treatment for 10-40 min, centrifuging the supernatant at 8000-12000 rpm for 10min, taking 2.4-5.6 mL of supernatant into a round bottom flask of 25 mL, carrying out rotary evaporation at 35-45 ℃, adding 1 mL of methanol for redissolution, and passing through an organic filter membrane of 0.22 mu m for HPLC-DAD analysis.
(5) And (4) detecting the sample.
Taking 0.5 g of sample, respectively adding high, medium and low concentration levels of AA-I and AA-II mixed standard solutions, treating the sample according to the sample pretreatment method, performing liquid chromatography analysis, and calculating the sample standard recovery rate.
The invention has the beneficial effects that: the invention designs a method for simultaneously detecting aristolochic acid I and aristolochic acid II in houttuynia cordata based on a metal organic framework material (MIL-101(Fe)) dispersed solid-phase extraction combined with a high performance liquid chromatography technology. The metal organic framework material (MIL-101(Fe)) prepared by the invention has good adsorption and enrichment effects on target detection substances (AA-I and AA-II), and the detection method of aristolochic acid (AA-I and AA-II) in houttuynia cordata established based on the material is accurate, reliable and high in sensitivity, and provides a technical means for safety evaluation of houttuynia cordata medicinal materials.
Drawings
FIG. 1 XRD spectrum of MIL-101(Fe) prepared in example 1;
FIG. 2 scanning electron micrograph of MIL-101(Fe) prepared in example 1;
FIG. 3 pore size distribution plot of MIL-101(Fe) prepared in example 1;
FIG. 4 chromatogram of AA-I and AA-II of example 2: 1. AA-II (1 mg/L); 2. AA-I (1 mg/L).
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Weighing 1.100 g H2BDC, dispersed in 70 mL DMF, stirred for 20 min, added 2.432 g FeCl3·6H2O, stirring for 30 min, and mixing the solutionThe mixture was transferred to a 100 mL polytetrafluoroethylene autoclave and heated at 110 ℃ for 24 hours. Centrifuging at 10000 rpm for 10min, discarding supernatant, washing the product with DMF and methanol sequentially for 3 times, and vacuum drying at 70 deg.C for 12 h. The X-ray diffraction pattern, the scanning electron micrograph and the pore size distribution of the sample are shown in the figure 1, the figure 2 and the figure 3 in sequence. The X-ray diffraction test result shows that MIL-101(Fe) is successfully synthesized, and the crystallinity is good; the scanning electron microscope shows that the crystal particles of the material have a specific regular octahedral structure and are uniform in size; physical adsorption tests are carried out on the material, and the pore size distribution calculated by a non-local density functional model shows that the prepared MIL-101(Fe) has the pore size distribution concentrated at 1.7 nm, 2.8 nm and 4.5 nm.
Example 2
The method adopts an American Agilent1290 high performance liquid chromatograph, and the chromatographic conditions are as follows: a chromatographic column: a C18 column (4.6 mm. times.250 mm. times.5 μm); column temperature: 25 ℃, injection volume: 10 mu L of the solution; mobile phase: acetonitrile-0.1% aqueous acetic acid (60: 40, v/v); flow rate: 1 mL/min; detection wavelength: 254 nm. The chromatogram of the AA-I and AA-II mixed standard solution is shown in FIG. 4.
Example 3
Preparing a series of AA-I and AA-II mixed standard solutions with mass concentration by using methanol as a solvent, measuring under the liquid chromatography condition, performing linear regression on the mass concentration X by using the peak area Y of each component (shown in table 1), wherein the linear relation between AA-I and AA-II is good within the range of 0.05-20 mg/L (R is the linear relation between AA-I and AA-II)2= 0.9999), detection Limit (LOD) 0.007 mg/L and 0.014 mg/L, respectively, and quantification Limit (LOQ) 0.024 mg/L and 0.045 mg/L, respectively.
TABLE 1 linear equations, detection limits and quantitation limits for AA-I and AA-II
Example 4
Pulverizing dried herba Houttuyniae sample, sieving with 80 mesh sieve, weighing 0.5 g (accurate to 0.001 g) herba Houttuyniae powder sample, adding 10 mL methanol, performing ultrasonic treatment for 30 min, centrifuging at 6000 rpm for 10min, collecting 1 mL supernatant, adding 40 mg of MIL-101(Fe) obtained by preparation, performing vortex for 20 min, centrifuging at 11000 rpm for 8 min, discarding supernatant, adding 5 mL acetone (containing 0.2% glacial acetic acid), performing ultrasonic treatment for 20 min, centrifuging at 8000 rpm for 10min, collecting 4 mL supernatant to 25 mL round bottom flask, performing rotary evaporation at 45 deg.C, adding 1 mL methanol for redissolution, filtering with 0.22 μm organic filter membrane, and analyzing with HPLC-DAD.
Example 5
Weighing 0.5 g of sample, respectively adding high, medium and low concentration levels of mixed standard solutions of AA-I and AA-II, treating the sample according to the sample pretreatment method, performing HPLC-DAD analysis, and calculating the sample standard addition recovery rate and precision, wherein the results are shown in Table 2.
TABLE 2 recovery and precision (n = 6) with calibration
ND is below the detection limit
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It should be understood by those skilled in the art that various changes and substitutions may be made in accordance with the technical solution and the inventive concept of the present invention, and the same properties or uses should be considered as the protection scope of the present invention.
Claims (2)
1. A method for detecting aristolochic acid in houttuynia cordata based on metal organic framework material MIL-101(Fe) by adopting a DSPE method and combining an HPLC-DAD technology is characterized by mainly comprising the following steps:
(1) preparing a metal organic framework material MIL-101 (Fe);
(2) liquid chromatography conditions;
(3) simultaneously detecting aristolochic acid I (AA-I) and aristolochic acid II (AA-II);
(4) pretreating a sample;
(5) and (4) detecting the sample.
2. A method for detecting aristolochic acid in houttuynia cordata based on a metal organic framework material MIL-101(Fe) by adopting a dispersive solid-phase extraction method and combining a high performance liquid chromatography technology is characterized by mainly comprising the following steps:
(1) preparation of Metal organic framework Material MIL-101(Fe)
Weighing 0.622-1.106 g terephthalic acid (H)2BDC) is dispersed in 40-70 mL of N, N-Dimethylformamide (DMF), stirred for 10-30 min, and added with 2.026-3.244 g of ferric chloride hexahydrate (FeCl)3·6H2O), continuously stirring for 30-60 min, then transferring the solution into a 100 mL polytetrafluoroethylene autoclave, and heating for 10-24 h at 110-130 ℃; centrifuging at 8000-12000 rpm for 10min, removing supernatant, washing the product with DMF and methanol in sequence, and vacuum drying at 60-70 ℃ for 12h to obtain a product;
(2) conditions of liquid chromatography
A chromatographic column: a C18 column (4.6 mm. times.250 mm. times.5 μm); column temperature: 25 ℃; sample introduction volume: 10 mu L of the solution; mobile phase: acetonitrile-0.1% aqueous acetic acid (60: 40, v/v); flow rate: 1 mL/min; detection wavelength: 254 nm;
(3) simultaneous detection of aristolochic acid I (AA-I) and aristolochic acid II (AA-II)
Preparing a series of AA-I and AA-II mixed standard solutions with mass concentration by using methanol as a solvent, measuring under the condition of the liquid chromatography, performing linear regression on the mass concentration X by using the peak area Y of each component, and ensuring that the linear relation between AA-I and AA-II is good (R is within the range of 0.05-20 mg/L) (R is2Not less than 0.9999), the detection Limit (LOD) is 0.007 mg/L and 0.014 mg/L respectively, and the quantification Limit (LOQ) is 0.024 mg/L and 0.045 mg/L respectively;
(4) sample pretreatment
Crushing a dried houttuynia cordata sample, sieving the crushed houttuynia cordata sample by a sieve of 80-100 meshes, weighing 0.5 g (accurate to 0.001 g) of houttuynia cordata powder sample, adding 10 mL of methanol, carrying out ultrasonic treatment for 30 min, centrifuging the crushed houttuynia cordata sample at 6000-10000 rpm for 10min, taking supernatant, dispersing 20-100 mg of MIL-101(Fe) in 1 mL of supernatant, carrying out vortex oscillation for 10-40 min, centrifuging the supernatant at 8000-12000 rpm for 10min, discarding the supernatant, adding 3-10 mL of acetone containing 0.1-1.0% (v/v) of glacial acetic acid, carrying out ultrasonic treatment for 10-40 min, centrifuging the supernatant at 8000-12000 rpm for 10min, taking 2.4-5.6 mL of supernatant into a round bottom flask of 25 mL, carrying out rotary evaporation at 35-45 ℃, adding 1 mL of methanol for redissolution, and passing through an organic filter membrane of 0.22 mu m for HPLC-DAD analysis;
(5) detection of samples
Taking 0.5 g of sample, respectively adding high, medium and low concentration levels of AA-I and AA-II mixed standard solutions, treating according to the sample pretreatment method, performing liquid chromatography, and calculating the sample standard recovery rate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078612A (en) * | 2022-06-01 | 2022-09-20 | 长沙理工大学 | Analysis method for detecting chemicals based on modified Cr-MOF |
| CN117471003A (en) * | 2023-12-28 | 2024-01-30 | 中国中医科学院中药研究所 | Separation and quantitative detection method for aristolochic acid component in houttuynia cordata and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115078612A (en) * | 2022-06-01 | 2022-09-20 | 长沙理工大学 | Analysis method for detecting chemicals based on modified Cr-MOF |
| CN117471003A (en) * | 2023-12-28 | 2024-01-30 | 中国中医科学院中药研究所 | Separation and quantitative detection method for aristolochic acid component in houttuynia cordata and application thereof |
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