CN108613952A - A kind of analysis determining method of myricetin - Google Patents
A kind of analysis determining method of myricetin Download PDFInfo
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- G—PHYSICS
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Abstract
A kind of analysis determining method of myricetin, comprises the step of the preparation of sample solution to be tested, and standard sample solution, ZrOCl is added in the preparation of standard sample solution in volumetric flask2Solution and buffer solution, deionized water constant volume scan fluorescence spectrum using sepectrophotofluorometer, measureλ ex/λ emThe fluorescence intensity of=460/545 nmI F , draw using myricetin standard concentration as abscissa, fluorescence intensity level is the myricetin standard curve of ordinate, and equation of linear regression is recycled to calculate the concentration of myricetin in sample solution.This method uses the content of myricetin in fluorescence spectrum method for measuring vine tea, simple and efficient to handle, as a result accurately, can effectively avoid the interference of analogue dihydromyricetin.
Description
Technical field
The present invention relates to a kind of assay methods of myricetin, belong to technical field of analytical chemistry.
Background technology
Myricetin, also known as myricetin, myricetin belong to flavonoid drugs, are prevalent in pulse family
(Leguminosae), the plants such as Primulaceae (Primulaceae), Vitaceae (Vitaceae), composite family (Compositae)
In.It is mainly derived from the leaf of Myruca ceas red bayberry spp.ing plant red bayberry Myrica rubra (Lour) Sieb.et Zucc., skin,
The extract of root etc.;Red bayberry is one of subtropical fruit tree originating in China, is distributed mainly on the ground such as Ningbo Yuyao and Cixi.Red bayberry
There are many physical and chemical effects for active constituent myricetin in bark and leaf:(1) antagonism of platelet activating factor (PAF),
With antithrombotic, various cardiovascu- lar effects such as resist myocardial ischemia, improve microcirculation, (2) hypoglycemic effect;(3) resist
Oxidation;(4) liver protection function;(5) spasmolysis ethylism;In addition to the above-mentioned pharmacological action having verified that, also have anti-
Scorching, antitumor, anti-mutation, eliminates the multiple pharmacological effects such as interior free yl at pre- anti-caries, inoxidizability.The structure of myricetin
General formula is
The method of detection myricetin mainly has high performance liquid chromatography, ultraviolet spectrophotometry etc., Chinese patent at present
A kind of method measuring each ingredient of flavonoids in 11 in vine tea with HPLC is introduced in 201610079019.9, it utilizes high pressure liquid phase
Chromatography can detect the Flavonoid substances such as dihydromyricetin, dihydroquercetin, aromadendrin, myricetin, but use high pressure liquid phase color
The speed of chromatography detection is slow, drug, solvent consumption are big, and the suction due to myricetin and dihydromyricetin in the case where measuring wavelength
Luminosity interferes with each other, inaccurate using ultraviolet spectrophotometry analysis result.
Invention content
The purpose of the present invention is to provide a kind of analysis determining method of myricetin, by myricetin in vine tea sample with
ZrOCl2The product with fluorescence is complexed into, the content of myricetin is calculated using fluorescent spectrometry, the method has operation letter
Just the feature quick, result is accurate, stability is good.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of analysis determining method of myricetin, it includes the following steps:
A, test sample is prepared:Vine tea powder accurately is weighed, is impregnated with a small amount of methanol, is taken supernatant, arrived with methanol constant volume
In brown volumetric flask, the vine tea sample solution of a concentration of 1.00-2.00mg/mL is obtained;
B, standard sample is prepared:Myricetin standard items are weighed, the serial myricetin of various concentration is configured to methanol dissolving
Standard solution;
C, standard curve is drawn:It is separately added into CH in several volumetric flasks3COONa-CH3COOH buffer solutions and ZrOCl2It is molten
Liquid, then be separately added into serial myricetin standard solution made from step b and shaken up with deionized water constant volume, with glimmering after placement 1h
Light spectrophotometer scans fluorescence spectrum, measures λex/λemThe fluorescence intensity I of=460/545nmF, with the dense of myricetin standard items
Degree is abscissa, and fluorescence intensity level is that ordinate makees myricetin standard curve, obtains the linear of fluorescence intensity and standard concentration
Regression equation, IF=-0.29+1999.78c;
D, determination sample:Test sample solution made from step a is added in volumetric flask, repeats step c, scans fluorescence light
Spectrum measures sample to be tested in λex/λemThe fluorescence intensity of=460/545nm calculates poplar in sample solution using equation of linear regression
The concentration of syphilis.
The pH value of reaction solution is 4.0- after constant volume in the analysis determining method of above-mentioned myricetin, the step c and step d
4.5。
The analysis determining method of above-mentioned myricetin, the ZrOCl2Solution is the dichloro oxygen that mass percent concentration is 2%
Change zirconium methanol solution, ZrOCl in reaction solution2A concentration of 7.2 × 10-3-9.1×10-3mol/L。
Methanol content is less than in the reaction solution of the analysis determining method of above-mentioned myricetin, the step c and step d
20%.
Vine tea powder is soaked in 10mL methanol in the step a by the analysis determining method of above-mentioned myricetin, and 50 DEG C super
Sound dissolves 30min, stands for 24 hours, centrifuging and taking supernatant is in 25mL brown volumetric flasks, methanol constant volume, obtains vine tea sample solution.
The present invention is complexed using myricetin in zirconium oxychloride and sample into the product with fluorescence, then uses fluorescent spectrometry
Standard curve is generated, equation of linear regression is acquired, to calculate the content of myricetin.Utilize ZrOCl2Sensitized fluorescence is analyzed
Red bayberry cellulose content is a kind of method of completely new detection myricetin in vine tea, is provided fast and accurately for vine tea quality evaluation
Reference data, can be applied to actual sample such as vine tea, red bayberry branches and leaves in myricetin detection.The above method is easy to operate, only
It need to be by vine tea extracting solution and ZrOCl2Solution mixes under conditions of having buffer solution, and scanning fluorescence spectrum, which can be analyzed, obtains it
In myricetin content.Its analyze speed is fast simultaneously, reaction sensitivity is high, and the limitation of detection is only 3.3ng/mL, only
There is the one thousandth of the concentrations of 3.1 μ g/mL of high-pressure liquid phase method.
Fluorescence method has the characteristics that high selectivity, due to dihydromyricetin and ZrOCl2Solution does not react, can be complete
The whole district divides the analogue dihydromyricetin in sample, to avoid dihydromyricetin in fluorescence spectrophotometry from being tied to measuring
The interference of fruit, measurement result is accurate, data reappearance is good.
Description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the triaxial stress condition of standard solution myricetin (A) of the present invention;
Fig. 2 is the triaxial stress condition of inventive samples solution vine tea (B);
Fig. 3 is the triaxial stress condition of myricetin series standard solution of the present invention;
Fig. 4 is the triaxial stress condition of vine tea sample solution of the present invention;
Fig. 5 is the triaxial stress condition of vine tea sample mark-on serial solution of the present invention;
Fig. 6 is the fluorescence method canonical plotting of myricetin of the present invention;
Fig. 7 is the fluorescence method mark-on curve graph of myricetin of the present invention;
Fig. 8 is the chromatography canonical plotting of myricetin of the present invention;
Fig. 9 is the chromatography mark-on curve graph of myricetin of the present invention.
Specific implementation mode
A kind of assay method of myricetin of the present invention, includes the following steps:
A, test sample is prepared:The accurate vine tea powder for weighing crushing is soaked in 25mL brown volumetric flasks with a small amount of methanol
Bubble, 50 DEG C of ultrasonic dissolutions extract 30min, and standing centrifuges, takes supernatant, in methanol constant volume to 25mL brown volumetric flasks, obtain for 24 hours
The vine tea sample solution of a concentration of 1.00-2.00mg/mL.The methanol is absolute methanol.
B, standard sample is prepared:Myricetin standard items accurately are weighed in brown volumetric flask, are dissolved and are determined with absolute methanol
Hold to scale, obtains the myricetin standard items storing solution of a concentration of 1.00-10.00 μ g/mL.By myricetin standard items storing solution according to
Gradient dilution is at a series of myricetin standard solutions.The concentration gradient of serial standards solution ranging from 0.05-0.5 μ g/mL.
C, standard curve is drawn:A concentration of 2% ZrOCl of certain volume is separately added into several 10mL volumetric flasks2
Solution and CH3COONa-CH3COOH buffer solutions, then be separately added into made from step b serial myricetin standard solution, spend from
Sub- water constant volume, shakes up, and the pH value of solution is adjusted to 4.2 or so.Sepectrophotofluorometer is used to scan fluorescence spectrum after placing 1h,
Measure λex/λemThe fluorescence intensity I of=460/545nmF, with a concentration of abscissa of myricetin standard items, fluorescence intensity level is vertical
Coordinate makees myricetin canonical plotting, and standard concentration and fluorescence intensity I are obtained according to canonical plottingFEquation of linear regression.
The ZrOCl2Solution is the zirconium oxychloride methanol solution that mass percent concentration is 2%.
The scanning range of the fluorescence spectrum is λex:330-550nm, λem:480-630nm, sweep spacing are set as 5nm,
Slit width is ex/em:5.0/5.0, sweep speed 12000nm/min.
D, determination sample solution:Test sample solution made from the step a of certain volume is taken to be added in 10mL volumetric flasks,
Add 2% ZrOCl2Solution and CH3COONa and CH3COOH buffer solutions are shaken up with deionized water constant volume, make the pH of solution
Value is adjusted to 4.2.It uses sepectrophotofluorometer to scan fluorescence spectrum after placing 1h, measures λex/λem=460/545nm's is glimmering
Luminous intensity IF.The concentration of myricetin in test sample solution is calculated using the equation of linear regression that step c is obtained.
For the pH ranges of reaction solution in 4.0-4.5, myricetin forms stable complex compound with Zr, is conducive to fluorescence spectrum
It measures.PH is too low when being less than 3.5, ZrOCl2With Zr in acidic environment4+In the presence of being not easy to combine with myricetin;PH is excessively tall and big
When 5.0, ZrOCl2It hydrolyzes, is reduced with the binding ability of myricetin, to which fluorescence reduces.
The ZrOCl2Solution is a concentration of 2% (w/w) zirconium oxychloride methanol solution.ZrOCl2Addition be anti-
It is 4.5 × 10 to answer its concentration range in solution-3-1.0×10-3Mol/L, ZrOCl2Concentration be preferably 7.2 × 10-3-9.1×
10-3mol/L.ZrOCl in the range of preferred concentration2The fluorescence intensity generated with myricetin is most strong and is held essentially constant.By
The content of methanol directly affects the fluorescence intensity of myricetin in solution, therefore the content that need to control methanol in reaction solution is less than
20%.
Myricetin and ZrOCl2Complex reaction occurs, forms the compound that fluorescence is strong and stablizes, is conducive to accurately carry out
Quantitatively fluorimetric analysis.The chemical equation of its complex reaction is
The vine tea sample solution of experimental concentration scans ultraviolet-visible absorption spectroscopy, absorbance of the sample solution at 460nm
It is 0.0311, is less than 0.05, therefore fluorescence data is used to ignore when analyzing the influence of interior filter effect.
Embodiment 1
One, the verification test of fluorescence method
The preparation of myricetin standard solution:Accurately 0.00123g myricetins standard items are weighed in 25mL brown volumetric flasks
In, constant volume is dissolved with methanol, obtains the myricetin storing solution of 49.2 μ g/mL, the used time is diluted to the poplar of 7.872 μ g/mL of respective concentration
Syphilis standard solution;
The preparation of vine tea sample solution:Vine tea sample is placed in oven and dried, smashes, accurately weighs vine tea powder
0.04030g is impregnated with 10mL absolute methanols, and 50 DEG C of ultrasonic dissolutions extract 30min, and standing centrifuges for 24 hours, takes supernatant in 25mL
In brown volumetric flask, in methanol constant volume 25mL brown volumetric flasks, the vine tea sample solution of 1612 μ g/mL is obtained.
ZrOCl2The preparation of solution:Take 1.6212g ZrOCl2In small beaker, absolute methanol dissolving is transferred to 100mL appearances
In measuring bottle, with absolute methanol constant volume, 2% (w/w) zirconium oxychloride methanol solution (molar concentration 0.091mol/L) is obtained.
The preparation of NaAc-HAc solution:Sodium acetate 4.1002g is weighed respectively, and glacial acetic acid 15.8mL is in small beaker with water-soluble
Solution, transfers in 25mL volumetric flasks, with water constant volume;Take sodium acetate solution, acetum 1.00mL in 250mL volumetric flasks respectively
In, it is diluted with water constant volume, obtains pH=4.2 buffer solutions.
Instrument:F-7000 sepectrophotofluorometers (Hitachi).
13 10mL volumetric flasks are taken, the NaAc-HAc solution of 1.00mL and the 2%ZrOCl of 1.00mL are separately added into2Methanol
Solution.2-6 volumetric flasks are separately added into myricetin standard solution, volume be respectively 0.1mL, 0.2mL, 0.3mL, 0.4mL,
0.5mL is configured to the serial standards solution of concentration gradient.7-13 volumetric flasks are separately added into 0.3mL vine tea solution, 10-13
Number volumetric flask is separately added into myricetin standard solution, and volume is respectively 0.1mL, 0.2mL, 0.3mL, 0.4mL, and wherein No. 1-6 is
Myricetin serial standards solution, No. 7-9 parallel vine tea extracting solution for same concentrations, 10-13 are serial mark-on solution, are prepared
In in each volumetric flask solution addition it is as shown in table 1.Methanol content is respectively less than 20% in each volumetric flask, deionized water constant volume,
It shakes up, controls the pH of solution 4.20 or so, three-dimensional fluorescence spectrum is scanned after placing 1 hour.Respectively obtain myricetin series mark
Quasi- solution triaxial stress condition, vine tea sample solution triaxial stress condition, vine tea sample mark-on serial solution triaxial stress condition,
As shown in Figure 2, Figure 3, Figure 4.
Table 1 is the compound concentration list position μ g mL of 13 test sample solutions-1
The triaxial stress condition of No. 6 and No. 7 volumetric flasks is taken to be analyzed, it will be seen from figure 1 that myricetin standard in A figures
The myricetin and ZrOCl of solution (No. 6 volumetric flasks)2Two fluorescence peaks, excitation wavelength lambda are generated after sensitizationexRespectively 280/
460nm, emission wavelength lambdaemIt is 545nm;Vine tea sample solution ZrOCl in Fig. 2 (B figures)2Equally in λ after sensitizationex/λem=
Occur a fluorescence peak, excitation wavelength lambda at 460/545nmexIt is because of extinction at 280nm not occur fluorescence peak at 280nm
Degree is too big, interior filter effect is produced, to shelter λex/λemFluorescence peak at=280/545nm.Since the two swashs long
Send out wavelength XexPosition for 460nm fluorescence peaks is completely superposed, and shape is coincide substantially, so ZrOCl is being added in vine tea extracting solution2First
The sensitized fluorescence generated after alcoholic solution is exactly the sensitized fluorescence of myricetin and Zr complexings, it is possible to use red bayberry with fluorescence method
Element measures the content of myricetin in vine tea as standard.
Two, the content of myricetin in vine tea is measured using calibration curve method
The three-dimensional collection of illustrative plates obtained in Fig. 2 is handled, in the triaxial stress condition for reading myricetin standard serial solution
λex/λemFluorescence intensity at=460/545nm, data are as shown in table 2.With a concentration of abscissa of myricetin standard items, fluorescence
Intensity is the canonical plotting (Fig. 5) that ordinate makees myricetin.Standard concentration and fluorescence intensity are obtained according to canonical plotting
Equation of linear regression is IF=-0.29+1999.78c, 0.0787 μ g/mL-0.3936 μ g/mL of concentration range, coefficient R=
0.9998, the linear relationship of related coefficient close to the 1 above-mentioned regression equation of explanation is good.The myricetin concentration range of Fluorometric assay
For 0.07784-0.8757 μ g/mL.Detection limit D=3sb/ S=3*2.2/1999=0.0033 μ g/mL=3.3ng/mL.
The fluorescence intensity of 2 myricetin standard serial solution of table
As shown in figure 3, reading λ in vine tea sample triaxial stress conditionex/λemFluorescence intensity at=460/545nm, number
According to as shown in table 3.The average value of the fluorescence intensity of vine tea sample is brought into regression equation, obtains the average dense of myricetin in sample
Degree is c=0.1108 μ g/mL, calculate in vine tea the average content of myricetin be 0.2292%, standard deviation as a result is
0.2903%.
Myricetin assay in 3 vine tea of table
Three, the content of myricetin in Standard Addition Method for Determination vine tea is utilized
The three-dimensional collection of illustrative plates obtained in Fig. 4 is handled, the triaxial stress condition of vine tea sample mark-on serial solution is read
Fluorescence intensity (table 4) at middle 460nm/545nm, a concentration of abscissa of standard items is added, fluorescence intensity is made for ordinate
Figure, obtains myricetin mark-on curve graph (Fig. 6), and linear time that standard concentration and fluorescence intensity is added is acquired according to mark-on curve
Return equation.The equation of linear regression of mark-on curve is IF=225.3+2004.06504c, coefficient R=0.9997.Using outer
Pushing manipulation is it is found that work as IFWhen=0, the value of abscissa is the concentration of myricetin in sample, and c=0.1124 μ are obtained by regression equation
G/mL, the content for calculating myricetin in vine tea are 0.2325%.It is 0.2292% by the result that calibration curve method measures, two kinds of sides
The quantitative result that method measures is almost the same, meets the requirement of data analysis.
The recovery of standard addition of 4 vine tea of table
By table 4, the result shows that, the rate of recovery of mark-on method is 101.3%, within range 95.0%-105.0%, standard deviation
Difference is 2.17%, shows that this method has preferable reliability and accuracy.
Embodiment 2
One, high performance liquid chromatography examines the content of myricetin in vine tea
Myricetin standard solution:0.00640g myricetins standard items accurately are weighed in 25mL brown volumetric flasks, and methanol is fixed
Hold, obtain the myricetin storing solution of 256 μ g/mL, when use dilutes.
Vine tea sample solution:The accurate vine tea powder 1.28752g weighed in embodiment 1 is used in 25mL brown volumetric flasks
Methanol impregnates, 50 DEG C of ultrasound 30min, methanol constant volume, stands for 24 hours, obtains the vine tea sample solution of 51.50mg/mL, take supernatant
Centrifugation, when use, dilute.
Instrument:Chromatographic column:Agilent Zorbax SB-C18 chromatographic columns (150mm × 4.6mm, 5 μm);Mobile phase:First
Alcohol-water (0.045% phosphoric acid)=55:45;Detector:UV detector;Detection wavelength:370nm;Flow velocity:0.7mL/min;Column
Temperature:25℃;Sample size:5μL.
It takes the myricetin standard solution of different volumes in 10mL volumetric flasks respectively, is at concentration range with methanol dilution
0.5120-3.072 μ g/mL standard solution, sample introduction, is detected using high pressure lipuid chromatography (HPLC) successively.It is molten with myricetin standard
A concentration of abscissa of liquid, chromatographic peak area are ordinate, obtain chromatography canonical plotting (Fig. 7), carry out linear regression and obtain
To linear equation:A=-3.79+40.15c (μ g/mL), r=0.9998.It can be seen from the figure that in this concentration range, poplar
Good linear relationship is presented with mass concentration in the peak area of syphilis.
The vine tea sample 1.50mL of a concentration of 206 μ g/mL is separately added into 10mL volumetric flasks, with methanol constant volume, dilution
At the sample solution of the vine tea extracting solution of a concentration of 20.6 μ g/mL, chromatographic isolation is carried out under above-mentioned chromatographic condition, can reach base
Line detaches.The chromatogram of analysis myricetin standard items and vine tea sample solution can be seen that the retention time of myricetin standard items
For 5.665min, the retention time of vine tea sample solution is 5.660min under the same terms, therefore chromatographic peak herein is vine tea
The chromatographic peak of middle myricetin.Three times by the parallel sample introduction of vine tea sample, the peak area for recording myricetin respectively takes the flat of result three times
Mean value calculates the content of myricetin in vine tea according to the equation of linear regression obtained, the results are shown in Table 5.
The content of myricetin in 5 chromatography determination vine tea sample of table
As shown in Table 5, the content of myricetin is 0.2256% in Syrups by HPLC vine tea, the vine tea of fluorescence spectrometry
The content 0.2292% of middle myricetin, the testing result of two methods is relatively.
Two, the rate of recovery of high performance liquid chromatography
It is separately added into the vine tea sample 1.50mL of a concentration of 206 μ g/mL in 4 10mL volumetric flasks, then is separately added into dense
Degree is myricetin standard solution 0mL, 0.2mL, 0.4mL, 0.6mL of 25.6 μ g/mL, methanol constant volume, successively 5 μ of automatic sampling
L.Using the quality of the myricetin of addition as abscissa, chromatographic peak area is ordinate, obtains mark-on linear relationship chart (Fig. 8), adds
The linear equation of mark song line is:A=24.62+3.76m (μ g), r=0.9999.
The myricetin rate of recovery in 6 chromatography determination vine tea sample of table
By the result of calculation of table 6 it is found that the recovery of standard addition of myricetin is good in vine tea sample.
Claims (5)
1. a kind of analysis determining method of myricetin, which is characterized in that it includes the following steps:
A, test sample is prepared:It accurately weighs vine tea powder to be impregnated with a small amount of methanol, takes supernatant, held with methanol constant volume to brown
In measuring bottle, the vine tea sample solution of a concentration of 1.00-2.00 mg/mL is obtained;
B, standard sample is prepared:Myricetin standard items are weighed, the serial myricetin standard of various concentration is configured to methanol dissolving
Product solution;
C, standard curve is drawn:It is separately added into CH in several volumetric flasks3COONa-CH3COOH buffer solutions and ZrOCl2Solution, then
It is separately added into serial myricetin standard solution made from step b to be shaken up with deionized water constant volume, be divided with fluorescence after placing 1 h
Light photometer scans fluorescence spectrum, measures λex/λemThe fluorescence intensity of=460/545 nmI F , with a concentration of of myricetin standard items
Abscissa, fluorescence intensity level are that ordinate makees myricetin standard curve, obtain the linear regression of fluorescence intensity and standard concentration
Equation,
I F= -0.29+1999.78c;
D, determination sample:Test sample solution made from step a is added in volumetric flask, repeats step c, scans fluorescence spectrum,
Sample to be tested is measured to existλ ex/λ emThe fluorescence intensity of=460/545 nm calculates red bayberry in sample solution using equation of linear regression
The concentration of element.
2. the analysis determining method of myricetin according to claim 1, which is characterized in that fixed in the step c and step d
The pH value of reaction solution is 4.0-4.5 after appearance.
3. the analysis determining method of myricetin according to claim 2, which is characterized in that the ZrOCl2Solution is quality
The zirconium oxychloride methanol solution that percent concentration is 2%, ZrOCl in reaction solution2A concentration of 7.2 × 10-3- 9.1×10-3 mol/L。
4. the analysis determining method of myricetin according to claim 3, which is characterized in that the step c's and step d is anti-
Methanol content in solution is answered to be less than 20%.
5. according to the analysis determining method of claim 1-4 any one of them myricetins, which is characterized in that in the step a
Vine tea powder is soaked in 10mL methanol, 50 DEG C of 30 min of ultrasonic dissolution, stands 24 h, centrifuging and taking supernatant is in 25 mL palm fibres
In color tolerance measuring bottle, methanol constant volume obtains vine tea sample solution.
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Cited By (4)
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| CN110542664A (en) * | 2019-09-09 | 2019-12-06 | 湖北省农业科学院中药材研究所 | Method for detecting content of total flavonoids in vine tea |
| CN111995766A (en) * | 2020-09-13 | 2020-11-27 | 仲恺农业工程学院 | Method for preparing dihydromyricetin zinc nanoparticles based on vine tea extract and application thereof |
| CN115015362A (en) * | 2022-05-26 | 2022-09-06 | 广西壮族自治区农业科学院 | Electrochemical method for detecting myricetin |
| CN115201173A (en) * | 2022-07-29 | 2022-10-18 | 江苏省扬州环境监测中心 | Method for determining anionic surfactant in water based on three-dimensional fluorescence |
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| CN110542664A (en) * | 2019-09-09 | 2019-12-06 | 湖北省农业科学院中药材研究所 | Method for detecting content of total flavonoids in vine tea |
| CN111995766A (en) * | 2020-09-13 | 2020-11-27 | 仲恺农业工程学院 | Method for preparing dihydromyricetin zinc nanoparticles based on vine tea extract and application thereof |
| CN115015362A (en) * | 2022-05-26 | 2022-09-06 | 广西壮族自治区农业科学院 | Electrochemical method for detecting myricetin |
| CN115015362B (en) * | 2022-05-26 | 2024-01-12 | 广西壮族自治区农业科学院 | Electrochemical method for detecting myricetin |
| CN115201173A (en) * | 2022-07-29 | 2022-10-18 | 江苏省扬州环境监测中心 | Method for determining anionic surfactant in water based on three-dimensional fluorescence |
| CN115201173B (en) * | 2022-07-29 | 2024-03-12 | 江苏省扬州环境监测中心 | Method for measuring anionic surfactant in water based on three-dimensional fluorescence |
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