CN114113365B - Liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater - Google Patents
Liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater Download PDFInfo
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Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater. The method of the invention comprises the following steps: (1) preparing erythromycin fermentation wastewater into a sample solution; (2) Detecting the sample solution by adopting ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a detection result of the antibiotic substances; wherein, the chromatographic conditions are as follows: the chromatographic column is a C18 column; the mobile phase comprises a weak polar phase and a strong polar phase, the weak polar phase is selected from methanol or acetonitrile, the strong polar phase is selected from ammonium formate aqueous solution, ammonium acetate aqueous solution, formic acid-ammonium formate solution or acetic acid-ammonium acetate solution, wherein the acid content is 0.01 per mill-0.5% by volume, and the ammonium salt concentration is 0.01M-0.5M. The method has the advantages of high accuracy, high sensitivity and strong specificity, can rapidly and effectively detect the total amount of antibiotic substances in the erythromycin fermentation wastewater, provides a detection method basis for water quality evaluation of the antibiotic fermentation wastewater discharge, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater.
Background
Erythromycin is a fourteen-membered macrolide antibiotic produced by streptomyces erythromyces, and erythromycin A is a main active ingredient, has a strong antibacterial effect on gram-positive bacteria, and has been widely used for preventing and treating various diseases of human beings and animals. Meanwhile, waste water generated in the processes of erythromycin fermentation production, various cleaning and extraction also contains erythromycin A and other erythromycin antibiotics, and the erythromycin A and the erythromycin antibiotics also have a certain degree of bacteriostasis, and if the erythromycin A and the erythromycin antibiotics are improperly treated, water pollution can be caused, and the potential risk of generating drug resistance genes can be caused.
At present, the pretreatment steps of the method for detecting the antibiotic residues in the wastewater of the microbial fermentation pharmaceutical industry are more complicated. For example, a method for detecting erythromycin residue in bacterial residues by using high performance liquid chromatography is provided in Chinese patent No. CN 107907616A. The pretreatment step of the method comprises repeated extraction of the organic reagent, and the extracting solution is required to be further degreased, extracted, blown by nitrogen and the like, so that the operation is complicated, and the detection cost is increased. In addition, the common high performance liquid chromatograph is provided with an ultraviolet detector for detection, and the sensitivity of the detector can not meet the requirements for detecting antibiotics such as erythromycin.
On the other hand, in the waste water generated in the erythromycin fermentation production, erythromycin A has a similar structure with the impurity components, and chromatographic separation is difficult to realize. At present, there are few data reports on research methods for simultaneously detecting erythromycin antibiotics in erythromycin fermentation wastewater, which cannot ensure environmental friendliness and safety in the erythromycin fermentation wastewater discharge process.
Disclosure of Invention
The invention overcomes the problems and establishes a rapid, accurate and high-sensitivity detection method for simultaneously detecting and analyzing erythromycin antibiotics in erythromycin fermentation wastewater.
A liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater comprises the following steps:
(1) Preparing erythromycin fermentation wastewater into a sample solution;
(2) Detecting the sample solution by adopting ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a detection result of the antibiotic substances;
wherein, the chromatographic conditions are as follows: the chromatographic column is a C18 column; the mobile phase comprises a weak polar phase and a strong polar phase, the weak polar phase is selected from methanol or acetonitrile, the strong polar phase is selected from ammonium formate aqueous solution, ammonium acetate aqueous solution, formic acid-ammonium formate solution or acetic acid-ammonium acetate solution, wherein the acid content is 0.01 per mill-0.5% by volume, and the ammonium salt concentration is 0.01M-0.5M.
Preferably, the antibiotic substance is at least one of erythromycin A, erythromycin B, erythromycin C, erythromycin F, erythromycin A enol ether, dehydrated erythromycin A and N-demethyl erythromycin A.
Preferably, the step (1) specifically includes the following steps:
(1.1) regulating the pH value of the erythromycin fermentation wastewater to 6-8;
and (1.2) centrifuging the wastewater with the pH adjusted, taking supernatant, and passing through a microporous filter membrane.
Preferably, in the step (1.1), formic acid or ammonia water is adopted to adjust the pH;
and/or, in the step (1.2), the microporous filter membrane is a microporous filter membrane with the thickness of 0.22-0.45 μm.
Preferably, in step (2), the chromatographic conditions further include: the chromatographic column is a C18 column, and the particle size of the filler is 1.7 mu m; the mobile phase takes methanol as a weak polar phase and 0.02M ammonium formate aqueous solution as a strong polar phase.
Preferably, in step (2), the chromatographic conditions further include: the elution process is gradient elution, and the elution program comprises an initial stage, an intermediate stage and an end stage, wherein the duration of the initial stage is 1.0-5.0 min, and the volume ratio of the weak polar phase in the initial stage is 10% -30%; the duration of the middle stage is 5.0-10.0 min, and the volume ratio of the weak polar phase in the middle stage is 50-95%; the duration of the tail stage is 2.0-10.0 min, and the volume ratio of the weak polar phase of the tail stage is 10-30%; and/or the flow rate is 0.2-0.4 mL/min; and/or the column temperature is 25-40 ℃; and/or the sample injection amount is 2-20 mu L.
Preferably, in step (2), the chromatographic conditions further include: the elution procedure is 0.00-1.00min,25% methanol, 1.50-8.50min,50% methanol, 8.51-12.00min,90% methanol, 12.01-15.00min,25% methanol;
and/or a flow rate of 0.25mL/min;
and/or, the column temperature is 35 ℃;
and/or the sample injection amount is 10 mu L.
Preferably, in step (2), the mass spectrometry conditions include: the ionization mode is an electrospray positive ion mode; and/or the ion source temperature is 150-200 ℃; and/or the temperature of the desolvation gas is 300-800 ℃; and/or the flow rate of the desolvation gas is 400-1000L/Hr; and/or the spraying voltage is 2.8-3.5 kv; and/or the taper hole voltage is 30-50V; and/or, collision voltage is 14-40V; and/or the scanning mode is a multi-reaction monitoring mode.
Preferably, in step (2), the mass spectrometry conditions include: the temperature of the ion source is 150 ℃; and/or the desolventizing gas temperature is 450 ℃; and/or, the desolvation gas flow is 800L/Hr; and/or the spray voltage is 3.2kv.
Preferably, in the step (2), the content of the antibiotic substance is calculated by using a standard curve method.
In the invention, the erythromycin fermentation wastewater refers to wastewater generated in fermentation, cleaning and extraction processes in the process of fermenting and producing erythromycin.
By adopting the technical scheme of the invention, the following beneficial effects are achieved:
1. according to the invention, through optimizing chromatographic conditions, erythromycin compounds and impurities with similar molecular structures in the erythromycin fermentation wastewater are successfully separated, so that qualitative and quantitative detection of various antibiotic compounds in the erythromycin fermentation wastewater is realized. In addition, the invention adopts liquid chromatography-tandem mass spectrometry for detection, and can effectively improve the sensitivity of detection. In the method, the detection limit of erythromycin A is 0.01 mug/L, the detection limit of dehydrated erythromycin A and erythromycin F is 0.05 mug/L, and the detection limit of erythromycin B, erythromycin C, N-norerythromycin A and erythromycin A enol ether is 0.10 mug/L. The labeled recovery rate of 7 antibiotics is between 85% and 110.0% when the labeled concentration levels are 5 times of detection limits respectively. In a word, the method established by the invention has high accuracy, high sensitivity and strong specificity, can rapidly and effectively detect the total amount of antibiotic substances in the erythromycin fermentation wastewater, and provides a detection method basis for water quality evaluation of the antibiotic fermentation wastewater discharge.
2. In the preferred scheme of the invention, the pretreatment method of the erythromycin fermentation wastewater only needs pH adjustment, centrifugation and filtration, and does not need solid-phase extraction and repeated solvent extraction, thus having simple and rapid operation and low cost.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a total ion flow diagram of a 7 antibiotic cocktail standard in example 1.
FIG. 2 is a total ion flow diagram of an erythromycin fermentation wastewater sample in example 1.
Detailed Description
In the following examples and experimental examples, the reagents and materials used were commercially available.
Example 1 detection of erythromycin fermentation wastewater
The embodiment comprises the following steps:
1) Sample solution preparation:
measuring 20mL of wastewater, regulating the pH to 6-8 by ammonia water or formic acid, centrifuging for 10min at 4000r/min, taking supernatant, and passing the supernatant through a microporous filter membrane with the thickness of 0.22 mu m to obtain a sample solution.
2) Drawing a standard curve:
preparing 7 antibiotics of erythromycin A, erythromycin B, erythromycin C, erythromycin F, erythromycin A enol ether, dehydrated erythromycin A and N-norerythromycin A into a mixed standard stock solution with the concentration of 1000 mug/mL, dissolving with a small amount of methanol, then fixing the volume with water and diluting the mixed standard stock solution step by step into a mixed standard working solution with the concentration of 1.0 mug/L, 5.0 mug/L, 25.0 mug/L, 100.0 mug/L and 500.0 mug/L, detecting and analyzing the mixed standard working solution by adopting a liquid chromatography-tandem mass spectrometry method, drawing a standard curve to obtain peak areas and corresponding standard working solution concentrations, and solving a regression equation and a correlation coefficient;
3) Detection and analysis: and (3) injecting the mixed standard working solution and the sample to be tested into a high performance liquid chromatograph, performing detection analysis by adopting a liquid chromatography-tandem mass spectrometry method, and then performing quantitative analysis according to an external standard.
In the steps 2) and 3), the instrument of the liquid chromatography-tandem mass spectrometry is an ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometer.
The chromatographic conditions are as follows: the column was a Waters-C18 column (2.1X105 mm,1.7 μm); the mobile phase is methanol and 0.02M ammonium formate; gradient elution, 0.00-1.00min,25% methanol, 1.50-8.50min,50% methanol, 8.51-12.00min,90% methanol, 12.01-15.00min,25% methanol; the flow rate is 0.25mL/min; the column temperature is 35 ℃; the sample loading was 10. Mu.L.
Mass spectrometry conditions: electrospray positive ion mode; the temperature of the ion source is 150 ℃; the temperature of the desolvation gas is 450 ℃; the flow rate of the desolvation gas is 800L/Hr; the spray voltage was 3.2kv; specific parameters of the test compounds are shown in the following table:
| compounds of formula (I) | Parent ion (m/z) | Qualitative rating (m/z) | Quantitative ion (m/z) | Taper hole voltage/V | Collision energy/V |
| Erythromycin A | 734.35 | 115.71 | 158.07 | 34 | 30 |
| Erythromycin B | 718.42 | 560.29 | 158.10 | 42 | 30 |
| Erythromycin C | 720.36 | 576.28 | 158.10 | 40 | 32 |
| Erythromycin F | 750.36 | 592.30 | 158.10 | 48 | 32 |
| Erythromycin A enol ether | 716.37 | 558.29 | 158.10 | 34 | 28 |
| Anhydroerythromycin A | 716.36 | 158.10 | 558.23 | 34 | 14 |
| N-desmethyl erythromycin A | 720.36 | 562.29 | 144.10 | 42 | 32 |
The total ion flow diagram of the 7 antibiotics mixed standard sample obtained in this example is shown in fig. 1, and the total ion flow diagram of the sample solution is shown in fig. 2.
The concentrations of 7 antibiotics were calculated by the external standard method as follows:
experimental example 1 methodological verification
1. Linear investigation
The regression equations and correlation coefficients of erythromycin A, erythromycin B, erythromycin C, erythromycin F, erythromycin A enol ether, anhydroerythromycin A and N-norerythromycin A were calculated according to the method of step 2) in example 1 and are shown in the following table:
| names of Compounds | Regression equation | Correlation coefficient r |
| Erythromycin A | Y＝397.49X+518.78 | 0.9995 |
| Erythromycin B | Y＝564.22X+385.48 | 0.9987 |
| Erythromycin C | Y＝397.48X+550.76 | 0.9991 |
| Erythromycin F | Y＝351.75X+779.98 | 0.9984 |
| Erythromycin A enol ether | Y＝68.44X+12.29 | 0.9987 |
| Anhydroerythromycin A | Y＝229.43X+356.18 | 0.9983 |
| N-desmethyl erythromycin A | Y＝140.31X+50.08 | 0.9997 |
From the data in the table, the linearity of 7 antibiotics was good.
2. Detection limit, quantitative limit and standard recovery rate
The detection limit was set at a sample concentration of 3 times the signal-to-noise ratio. The concentration of the sample at 10 times the signal to noise ratio was used as the limit of quantification. And (5) examining the labeling recovery rate when the labeling concentration level of the sample is 5 times of the detection limit. The results are shown in the following table:
as can be seen from the table, the standard adding recovery rate of 7 antibiotics is between 85% and 110.0%, and the requirements of accuracy and sensitivity of detecting the erythromycin fermentation wastewater can be met.
According to the embodiment and experimental example, the detection of the antibiotic substances in the erythromycin fermentation wastewater is realized by adopting the liquid chromatography-tandem mass spectrometry, the method has the advantages of high accuracy, high sensitivity and strong specificity, can rapidly and effectively detect the total amount of the antibiotic substances in the erythromycin fermentation wastewater, provides a detection method basis for the water quality evaluation of the antibiotic fermentation wastewater discharge, and has good application prospect.
Claims (8)
1. A liquid chromatography-tandem mass spectrometry detection method for antibiotics in erythromycin fermentation wastewater is characterized by comprising the following steps:
(1) Preparing erythromycin fermentation wastewater into a sample solution;
(2) Detecting the sample solution by adopting ultra-high performance liquid chromatography-tandem mass spectrometry to obtain a detection result of the antibiotic substances;
wherein, the chromatographic conditions are as follows: the chromatographic column is a C18 column, and the particle size of the filler is 1.7 mu m; the mobile phase comprises a weak polar phase and a strong polar phase, the weak polar phase is selected from methanol, the strong polar phase is selected from ammonium formate aqueous solution, ammonium acetate aqueous solution, formic acid-ammonium formate solution or acetic acid-ammonium acetate solution, wherein the acid content is 0.01 per mill-0.5% by volume, and the ammonium salt concentration is 0.01M-0.5M;
the elution process is gradient elution, the elution program is 0.00-1.00min,25% methanol, 1.50-8.50min,50% methanol, 8.51-12.00min,90% methanol, 12.01-15.00min,25% methanol;
the step (1) specifically comprises the following steps:
(1.1) regulating the pH value of the erythromycin fermentation wastewater to 6-8;
(1.2) centrifuging the wastewater with the pH value adjusted, taking supernatant fluid, and passing through a microporous filter membrane to obtain the wastewater;
the antibiotic substances are erythromycin A, erythromycin B, erythromycin C, erythromycin F, erythromycin A enol ether, dehydrated erythromycin A and N-demethyl erythromycin A.
2. The method of detecting according to claim 1, wherein: in the step (1.1), formic acid or ammonia water is adopted to adjust the pH;
and/or, in the step (1.2), the microporous filter membrane is a microporous filter membrane with the thickness of 0.22-0.45 μm.
3. The method of detecting according to claim 1, wherein: in step (2), the chromatographic conditions further comprise: the mobile phase was a strongly polar phase with 0.02M ammonium formate in water.
4. The method of detecting according to claim 1, wherein: in step (2), the chromatographic conditions further comprise: the flow rate is 0.2-0.4 mL/min; and/or the column temperature is 25-40 ℃; and/or the sample injection amount is 2-20 mu L.
5. The method of detecting according to claim 4, wherein: in step (2), the chromatographic conditions further comprise:
the flow rate is 0.25mL/min;
and/or, the column temperature is 35 ℃;
and/or the sample injection amount is 10 mu L.
6. The method of detecting according to claim 1, wherein: in step (2), the mass spectrometry conditions include: the ionization mode is an electrospray positive ion mode; and/or the ion source temperature is 150-200 ℃; and/or the temperature of the desolvation gas is 300-800 ℃; and/or the desolvation gas flow is 400-1000L/Hr; and/or the spray voltage is 2.8-3.5 kv; and/or the taper hole voltage is 30-50V; and/or a collision voltage of 14 to 40V; and/or the scanning mode is a multi-reaction monitoring mode.
7. The method of detecting according to claim 6, wherein: in step (2), the mass spectrometry conditions include: the temperature of the ion source is 150 ℃; and/or the desolventizing gas temperature is 450 ℃; and/or, the desolvation gas flow is 800L/Hr; and/or the spray voltage is 3.2kv.
8. The method of detecting according to claim 1, wherein: in the step (2), the content of the antibiotic substance is calculated by adopting a standard curve method.
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| CN109553645A (en) * | 2017-09-25 | 2019-04-02 | 联邦制药(内蒙古)有限公司 | A kind of method of low content Erythromycin A in extraction fermentation liquid |
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| CN109553645A (en) * | 2017-09-25 | 2019-04-02 | 联邦制药(内蒙古)有限公司 | A kind of method of low content Erythromycin A in extraction fermentation liquid |
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| Retrospective mass spectrometric analysis of wastewater-fed mesocosms to assess the degradation of drugs and their human metabolites;Laia Sabater-Liesa等;《Journal of Hazardous Materials》;20201226;124984 * |
| 国产硬脂酸红霉素口服固体制剂质量分析;傅蓉等;《中国抗生素杂志》;20190312(第03期);39-45 * |
| 超高效液相色谱-串联质谱法测定水中12种抗生素;张晓燕等;《中州大学学报》;20130820(第04期);114-117 * |
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