CN111175389A - Method for detecting zhongshengmycin F by high performance liquid chromatography - Google Patents
Method for detecting zhongshengmycin F by high performance liquid chromatography Download PDFInfo
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- CN111175389A CN111175389A CN201911156453.2A CN201911156453A CN111175389A CN 111175389 A CN111175389 A CN 111175389A CN 201911156453 A CN201911156453 A CN 201911156453A CN 111175389 A CN111175389 A CN 111175389A
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Abstract
The invention relates to a method for detecting zhongshengmycin F by high performance liquid chromatography, which adopts the following chromatographic conditions: a chromatographic column: taking alkylsilane bonded silica embedded with polar groups as a stationary phase; mobile phase: organic phase-aqueous phase; the flow rate is 0.5-1.5ml/min, and the detection wavelength is 190-210 nm; column temperature: 10-40 ℃; sample introduction amount: 5-20 muL; the detector adopts an ultraviolet detector or a diode array detector. The existing method adopts a bioassay method for quantification, and a method of pre-column derivation is used as a qualitative method, the chromatographic column and the mobile phase are matched for use, so that the good separation degree and accuracy are obtained, the zhongshengmycin F and the homologue with a similar structure are well separated by the detection method, and the detection accuracy of the zhongshengmycin F is improved; in the detection method, the probiotins F peak time is about 8.8 min.
Description
Technical Field
The invention belongs to the technical field of pesticide detection and analysis, and particularly relates to a method for detecting zhongshengmycin F by high performance liquid chromatography.
Background
Zhongshengmycin, the chemical name of which is streptothricins, is one of the earliest discovered antibiotics, among which streptothricins F was discovered as early as 1942 by the Waksman research group, but its chemical structure was not finalized by artificial total synthesis until 1982, in which the structural formula of the F component is as follows:
the chemical structure of zhongshengmycin is composed of three parts of streptadine lactam, gulosamine and lysine side chain, 7 main components with bactericidal activity are provided, the lysine quantity is named as streptothricin F, E, D, C, B, A and X from 1 to 7 respectively, the activity is integrally related with the lysine quantity, namely the activity is stronger when the lysine quantity is larger.
The zhongshengmycin has wide antibacterial spectrum, can resist gram-positive bacteria, gram-negative bacteria, mycobacteria, saccharomycetes and filamentous fungi, and has moderate toxicity to human and livestock. The currently and effectively registered zhongshengmycin raw medicines and preparations in China have 41 varieties, wherein 1 of 12 percent of zhongshengmycin raw medicine registered products and the other 40 of the zhongshengmycin raw medicines are wettable powder, granules, aqueous solutions and the like, and the mixed preparation occupies a large proportion and is mainly used for preventing and treating diseases such as apple ring spot, cucumber bacterial angular leaf spot, tomato bacterial wilt and the like.
The quality standard of the pesticide product is the technical basis for the production, inspection and quality assessment of the product, and the scientific and effective quality standard of the product is the technical guarantee for ensuring the stable prevention and treatment effect of the pesticide. Compared with the chemical synthetic pesticide, the agricultural antibiotic has the characteristics of low raw medicine content, complex components and the like, and has greater difficulty in developing a detection method. From the current published data, the existing effective zhongshengmycin products have 6 product quality standards which are enterprise standards, namely Q/KLSW013-2018 < 12% zhongshengmycin mother medicine > of FujiaKaili biological products limited company, Q/KLSW 033-2018 < 3% zhongshengmycin soluble agent >, Q/KLSW 030-2018 < 0.5% zhongshengmycin granule >, Q/XNDZ124-2016 < 3% zhongshengmycin wettable powder > of Fujian New agriculture and Zhengzhengzhengshengmycin limited company, Q/370202HYJ 373-2018 < 2.0% zhongshengmycin aqua > of Heliang pharmaceutical products limited company, Q/73023813-3.7-2017% zhongshengmycin aqua agent of Sichuan Jinzhu ecological agriculture science limited company, and the control indexes of zhongshengmycin in the 6 enterprise standards are biological potency respectively.
Biological potency as a control index is very common in early agricultural and medical antibiotic quality standards, but the biological potency method has great limitations, such as long analysis time, poor reproducibility among laboratories, many human interference factors, and the like. Even more fatal is that many mixed preparations of zhongshengmycin are available, and the mixing of two bactericidal active compounds, especially the mixing of two bactericidal active compounds with a bactericide with antibacterial activity has a great problem in terms of theory that the content of zhongshengmycin measured by a biological potency method is inaccurate and is not feasible.
The chromatography has the advantages of short analysis time, good result reproducibility, accurate quantification of specific compounds and the like, and the trend of replacing the biological titer method with the chromatography has become the quality standard of antibiotics in recent years. In the above industry standards, liquid chromatography pre-column derivatization is used as a method for identifying the zhongshengmycin, but obvious defects exist in the technical details of the method. One is that the OPA pre-column derived product is not specific, and the first peak in the standard is selected for quantification, which has great randomness, because the proportion of the product is not fixed, the reaction result of the same sample also has great difference, the pre-column derived requirement is that the reaction is carried out quantitatively, and the product is specific; secondly, fluorescence detection is adopted, but in the method, only the detection wavelength is given to be 360nm, and the fluorescence detection must have two key parameters of the excitation wavelength and the detection wavelength. Since identification methods must be listed as required in the quality standards of pesticide products, the listing of the methods may be primarily in a form that meets the quality standards of the products of the enterprise and is not practically feasible.
Zhongshengmycin F is similar to its homologues in structure and is susceptible to interference from some of the homologues in HPLC detection. There is therefore a great need in the art for a method for detecting zhongshengmycin F with good separation and short run-time.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for detecting zhongshengmycin F by using a high performance liquid chromatography, which can realize the separation of the zhongshengmycin F from other homologues, thereby achieving the control of the product quality.
The invention adopts the following technical scheme that a method for detecting zhongshengmycin F by high performance liquid chromatography adopts the following chromatographic conditions;
a chromatographic column: taking alkylsilane bonded silica gel of an embedded polar group as a stationary phase;
mobile phase: organic phase-aqueous phase;
flow rate: 0.5-1.5mL/min, preferably 1.0 mL/min;
detection wavelength: 190-210nm, preferably 200 nm;
column temperature: 10-40 ℃, preferably 30 ℃;
sample introduction amount: 5-20 muL, preferably 10 muL;
a detector: an ultraviolet detector or a diode array detector.
In a preferred embodiment of the present invention, the chromatographic column using the embedded polar group-containing alkylsilane bonded silica as the stationary phase is preferably a chromatographic column using the embedded polar group-containing octadecylsilane bonded silica as the stationary phase.
In a preferred embodiment of the present invention, the organic phase in the mobile phase is selected from one or more of methanol and acetonitrile.
In a preferred embodiment of the invention, the aqueous phase of the mobile phase further contains sodium heptanesulfonate at a concentration by mass ranging from 0.05% to 0.15%, preferably 0.1%.
In a preferred embodiment of the invention, the aqueous phase of the mobile phase also contains phosphoric acid, the concentration by mass of phosphoric acid being in the range 0.1% to 0.3%, preferably 0.1%.
In a preferred embodiment of the invention, the mobile phase has a volume ratio of organic phase to aqueous phase of from 0:100 to 30:70, preferably 20: 80.
In a preferred embodiment of the invention, the column is used in conjunction with a flow.
The method for detecting zhongshengmycin F by the high performance liquid chromatography is realized by the following steps:
(1) weighing a standard containing a proper amount of zhongshengmycin F, dissolving the standard in a 50mL volumetric flask by using pure water, fixing the volume, shaking up uniformly, and filtering a 0.45 mu m filter membrane for preparing a test standard solution;
(2) weighing a sample containing a proper amount of zhongshengmycin F, dissolving the sample in a 50mL volumetric flask by using pure water, performing constant volume and shaking up, and filtering a 0.45 mu m filter membrane for preparing a sample to be tested;
(3) and (3) injecting the sample to be tested and the sample solution to be tested into a high performance liquid chromatograph, and performing high performance liquid chromatography analysis according to the chromatographic conditions.
In a preferred embodiment of the invention, the purity of the standard is higher than 99.9%.
The existing method adopts a bioassay method for quantification, and a method of pre-column derivation is used as a qualitative method, compared with the prior art, the method has the advantages that the chromatographic column and the mobile phase are matched for use, so that the good separation degree and accuracy are obtained, the zhongshengmycin F and the homologue with the similar structure are well separated by the detection method, and the detection accuracy and the detection efficiency of the zhongshengmycin F are greatly improved; in the detection method, the probiotins F peak time is about 8.8 min.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a high performance liquid chromatogram of a Zhongshengmycin F sample isolated according to the conditions of example 1;
FIG. 2 is a high performance liquid chromatogram of a Zhongshengmycin F sample isolated according to the conditions of example 2;
FIG. 3 is a high performance liquid chromatogram of a Zhongshengmycin F sample isolated according to the conditions of example 3;
FIG. 4 is a linear relationship diagram of the analysis method of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to only the following examples.
Example 1
Experimental apparatus and conditions:
waters1525 high performance liquid chromatograph, Waters2489 ultraviolet detector;
a chromatographic column: c18 (150X 4.6mm, 5 μm) of an embedded polar group;
mobile phase: (0.1% sodium heptanesulfonate +0.1% phosphoric acid) aqueous solution: acetonitrile =80: 20;
flow rate: 1.0 mL/min;
detection wavelength: 200 nm;
column temperature: 30 ℃;
sample introduction amount: 10 muL.
The test steps are as follows:
weighing a standard containing 0.02g of zhongshengmycin F, dissolving the standard in a 50mL volumetric flask by using pure water, fixing the volume, shaking up uniformly, and filtering a filter membrane of 0.45 mu m for preparing a test standard solution;
weighing a sample containing 0.02g of zhongshengmycin F, dissolving the sample in a 50mL volumetric flask by using pure water, fixing the volume, shaking up, and filtering a filter membrane of 0.45 mu m for preparing a sample to be tested;
and (3) injecting the test sample and the sample solution to be tested into a high performance liquid chromatograph, performing high performance liquid chromatography analysis according to the chromatographic conditions, and recording a chromatogram. The results are shown in FIG. 1, and the peak-off time of the main peak of Zhongshengmycin F is 8.8min as shown in FIG. 1.
Example 2
Experimental apparatus and conditions:
waters1525 high performance liquid chromatograph, Waters2489 ultraviolet detector;
a chromatographic column: c18 (150X 4.6mm, 5 μm) of an embedded polar group;
mobile phase: (0.1% sodium heptanesulfonate +0.1% phosphoric acid) aqueous solution: acetonitrile =80: 20;
flow rate: 1.0 mL/min;
detection wavelength: 205 nm;
column temperature: 30 ℃;
sample introduction amount: 10 muL.
The test steps are as follows:
weighing a standard containing 0.02g of zhongshengmycin F, dissolving the standard in a 50mL volumetric flask by using pure water, fixing the volume, shaking up uniformly, and filtering a filter membrane of 0.45 mu m for preparing a test standard solution;
weighing a sample containing 0.02g of zhongshengmycin F, dissolving the sample in a 50mL volumetric flask by using pure water, fixing the volume, shaking up, and filtering a filter membrane of 0.45 mu m for preparing a sample to be tested;
and (3) injecting the test sample and the sample solution to be tested into a high performance liquid chromatograph, performing high performance liquid chromatography analysis according to the chromatographic conditions, and recording a chromatogram. The results are shown in FIG. 2, where the time to peak of the Zhongshengmycin F main peak is 8.8min, as shown in FIG. 2.
Example 3
Experimental apparatus and conditions:
waters1525 high performance liquid chromatograph, Waters2489 ultraviolet detector;
a chromatographic column: c18 (150X 4.6mm, 5 μm) of an embedded polar group;
mobile phase: (0.15% sodium heptanesulfonate +0.1% phosphoric acid) aqueous solution: acetonitrile =80: 20;
flow rate: 1.0 ml/min;
detection wavelength: 200 nm;
column temperature: 30 ℃;
sample introduction amount: 10 muL.
The test steps are as follows:
weighing a standard containing 0.02g of zhongshengmycin F, dissolving the standard in a 50mL volumetric flask by using pure water, fixing the volume, shaking up uniformly, and filtering a filter membrane of 0.45 mu m for preparing a test standard solution;
weighing a sample containing 0.02g of zhongshengmycin F, dissolving the sample in a 50mL volumetric flask by using pure water, fixing the volume, shaking up, and filtering a filter membrane of 0.45 mu m for preparing a sample to be tested;
and (3) injecting the test sample and the sample solution to be tested into a high performance liquid chromatograph, performing high performance liquid chromatography analysis according to the chromatographic conditions, and recording a chromatogram. The results are shown in FIG. 3, where the time to peak of the Zhongshengmycin F main peak is 8.8min, as shown in FIG. 3.
Linear correlation test of analytical methods
Weighing about 0.1g of Zhongshengmycin standard substance and a 50ml volumetric flask, dissolving with ultrapure water, fixing the volume, respectively transferring 1, 5, 8, 10 and 15 into 5 50ml volumetric flasks, dissolving and fixing the volume, and preparing Zhongshengmycin standard solution as shown in the table below. After the instrument is stable, sampling is carried out according to the concentration from low to high. And taking the mass concentration of the zhongshengmycin as a horizontal coordinate and the peak area as a vertical coordinate to prepare a standard curve.
The standard curve was measured as shown in table 1 below: y =10986x +302421, and the linear correlation coefficient is R2= 0.9995. The zhongshengmycin has good linear relation in the concentration range of 47.7 mu g/mL-715.8 mu g/mL. The linear relationship is shown in fig. 4.
TABLE 1 results of linear correlation experiments for analytical methods
Accuracy test of analytical methods
Weighing 5 samples from a Zhongshengmycin F sample with known mass fraction, respectively adding a certain amount of Zhongshengmycin standard sample, and analyzing according to the detection method of the invention, wherein the average recovery rate of Zhongshengmycin F is 99.45% as shown in Table 2.
TABLE 2 accuracy test results of analytical methods
Precision test of analytical methods
5 samples are accurately weighed from the same sample and analyzed according to the detection method of the invention, as shown in Table 3, the relative standard deviation of the zhongshengmycin F is 0.74 percent after being parallelly detected for 5 times under the detection method, and is less than the calculated value 1.139 of Horwitz equation 2 (1-0.5 logC) multiplied by 0.67, and the precision under the method is proved to meet the method confirmation requirement.
TABLE 3 precision test results of analytical methods
Sensitivity test of analytical methods
The sample A1 was diluted in a gradient (2-fold, 4-fold, 8-fold, 16-fold … …) and was gradually diluted until no active ingredient was detected. As shown in table 4, the data indicates: the minimum detection limit of the zhongshengmycin is about 3ppm, can meet the detection of common constants, and is suitable for the detection of a zhongshengmycin mother medicine and related preparation products.
TABLE 4 sensitivity test results of the analytical methods
The test results show that the detection method has higher accuracy and precision, good linear relation and wide sensitivity application range.
Compared with the existing liquid chromatography conditions, the liquid chromatography conditions of the invention have better separation degree for zhongshengmycin F, thereby ensuring the detection accuracy. The invention fills the blank of high performance liquid detection and quantification of zhongshengmycin, and simultaneously solves the defects of nonspecific pre-column derivative products, long analysis time of a bioassay method, poor reproducibility among laboratories and the like.
The above preferred embodiments are only for illustrating the patent content of the present invention, and other embodiments of the present invention are also possible, but those skilled in the art should be able to adopt the technical teaching of the present invention and equivalent alternatives or equivalent modifications and fall within the protection scope of the present invention.
Claims (10)
1. A method for detecting zhongshengmycin F by high performance liquid chromatography is characterized by adopting the following chromatographic conditions:
a chromatographic column: taking alkylsilane bonded silica gel of an embedded polar group as a stationary phase;
mobile phase: organic phase-aqueous phase;
flow rate: 0.5-1.5 ml/min;
detection wavelength: 190-210 nm;
column temperature: 10-40 ℃;
sample introduction amount: 5-20 muL;
a detector: an ultraviolet detector or a diode array detector.
2. The method according to claim 1, characterized in that the following chromatographic conditions are used: flow rate: 1.0 ml/min; detection wavelength: 200 nm; column temperature: 30 ℃; sample introduction amount: 10 muL.
3. The method according to claim 2, wherein the chromatographic column using the embedded polar group-containing alkylsilane bonded silica as the stationary phase and the chromatographic column using the embedded polar group-containing octadecylsilane bonded silica as the stationary phase.
4. The method according to any one of claim 3, wherein the organic phase in the mobile phase is selected from one or more of methanol and acetonitrile.
5. A process according to any one of claims 3, characterized in that the aqueous phase of the mobile phase also contains sodium heptanesulfonate, the mass concentration of sodium heptanesulfonate being in the range 0.05% -0.15%, preferably 0.1%.
6. The method according to any one of claims 3, characterized in that the aqueous phase of the mobile phase also contains phosphoric acid, the concentration by mass of phosphoric acid being in the range 0.1% to 0.3%, preferably 0.1%.
7. The process according to claim 3, wherein the mobile phase has an organic phase-aqueous phase volume ratio of from 0:100 to 30:70, preferably 20: 80.
8. A method according to claim 3, wherein the chromatographic column is used in conjunction with a flow.
9. The method according to any one of claims 1-8, characterized by the following steps:
(1) weighing a standard containing a proper amount of zhongshengmycin F, dissolving the standard in a 50mL volumetric flask by using pure water, fixing the volume, shaking up uniformly, and filtering a 0.45 mu m filter membrane for preparing a test standard solution;
(2) weighing a sample containing a proper amount of zhongshengmycin F, dissolving the sample in a 50mL volumetric flask by using pure water, performing constant volume and shaking up, and filtering a 0.45 mu m filter membrane for preparing a sample to be tested;
(3) and (3) injecting the sample to be tested and the sample solution to be tested into a high performance liquid chromatograph, and performing high performance liquid chromatography analysis according to the chromatographic conditions.
10. The method of claim 9, wherein said standard is greater than 99.9% pure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113896753A (en) * | 2021-11-16 | 2022-01-07 | 陕西麦可罗生物科技有限公司 | Method for efficiently separating zhongshengmycin from fermentation liquor |
| CN114276392A (en) * | 2021-12-28 | 2022-04-05 | 陕西麦可罗生物科技有限公司 | Zhongshengmycin F component mother medicine and preparation method thereof |
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| CN103901128A (en) * | 2014-03-27 | 2014-07-02 | 深圳诺普信农化股份有限公司 | Analysis method of Zhongshengmycin content |
| US20170304288A1 (en) * | 2013-11-20 | 2017-10-26 | Texas Southern University | Formulations of Methionine Aminopeptidase Inhibitors for Treating Infectious Diseases |
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| US20170304288A1 (en) * | 2013-11-20 | 2017-10-26 | Texas Southern University | Formulations of Methionine Aminopeptidase Inhibitors for Treating Infectious Diseases |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896753A (en) * | 2021-11-16 | 2022-01-07 | 陕西麦可罗生物科技有限公司 | Method for efficiently separating zhongshengmycin from fermentation liquor |
| CN114276392A (en) * | 2021-12-28 | 2022-04-05 | 陕西麦可罗生物科技有限公司 | Zhongshengmycin F component mother medicine and preparation method thereof |
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