CN103940937A - Method used for determining antibiotic content of food or environmental samples via accelerated solvent extraction online purification - Google Patents
Method used for determining antibiotic content of food or environmental samples via accelerated solvent extraction online purification Download PDFInfo
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- CN103940937A CN103940937A CN201410054464.0A CN201410054464A CN103940937A CN 103940937 A CN103940937 A CN 103940937A CN 201410054464 A CN201410054464 A CN 201410054464A CN 103940937 A CN103940937 A CN 103940937A
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Abstract
The invention discloses a method used for determining antibiotic content of food or environmental samples via accelerated solvent extraction online purification. The method comprises following steps: a, preparation of standard solutions; b, preparation of coordination polymers; c, online purification-accelerated solvent extraction of the coordination polymers; and d, determination of the standard solutions and the samples. Synthesis of copper terephthalate coordination polymer prepared via the method is easy to realize in laboratories; materials are easily available; online sample purification effects equal to that of existing commercial adsorbents on the copper terephthalate coordination polymer can be achieved, and effects are better than that of the existing commercial adsorbents; when the method is used for determination of antibiotic quantitative determination, the method is capable of increasing experimental accuracy and detection precision greatly, and ensuring data accuracy. The method used for determining antibiotic content of food or environmental samples via accelerated solvent extraction online purification is a novel antibiotic quantitative and qualitative detection method.
Description
Technical field
The present invention relates to chemical detection method art, refer in particular to a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample.
Background technology
In prior art, for most the employing as adsorbents such as Fo Luoli tripoli, silica gel, aluminium oxide of adsorbent of accelerated solvent in-line purification, these adsorbents lipid matrix composition in can adsorption sample etc., thereby reduce the impact on object molecule (as microbiotic) in instrument testing process of these matrix compositions, increased the response of object.
Microbiotic has vital role in treatment disease and agricultural production.But excessive use causes remaining in current food trace microbiotic, antibiotic common extracting method mainly contains liquid-liquid extraction, ultrasonic assisted extraction or Microwave-assisted Extraction and gets etc., but in these methods, sample matrices is often extracted in organic solvent together with object, the detection of object is brought to larger interference, can not carry out highly sensitive detection to trace materials.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, its fundamental purpose is to provide a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample.
For achieving the above object, the present invention adopts following technical scheme: a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample, comprise the steps,
The preparation of a, standard solution: get microbiotic standard specimen, be placed in volumetric flask, shake dissolving after adding a certain amount of solvent, carry out isochoric formation microbiotic standard specimen mother liquor with identical solvent; Microbiotic standard specimen mother liquor is adopted to the microbiotic standard solution of the method preparation variable concentrations of stepwise dilution;
The preparation of b, coordination polymer: terephthalic acid (TPA) and NaOH are added to the water, after abundant stirring and dissolving, add nitrate trihydrate copper, till being continuously stirring to and having blue powder shape precipitation generate in solution, cooling, filtration air-dry to obtain the terephthalic acid (TPA) copper complex of blue powder, be placed in brown wide-necked bottle by this blue powder for subsequent use;
C, coordination polymer in-line purification-accelerated solvent extraction: sample is pulverized with comminutor, after getting a certain amount of sample and terephthalic acid (TPA) copper complex and mixing, put into the abstraction pool of accelerated solvent extraction, under the temperature and pressure condition setting, carry out auto extractive; Liquid after extraction flows in receiving flask and collects, and this extract is passed through to constant volume at 50 DEG C of temperature, after rotary evaporation in vacuo, obtains sample extraction liquid;
The mensuration of d, standard solution and sample: the microbiotic standard solution that step a is prepared injects chromatographic analysis system and detects, and obtains microbiotic standard solution chromatogram; Then the extract in step c is injected to chromatographic analysis system and detect analysis, and convert and draw antibiotic content in sample according to the prepared standard equation of microbiotic standard solution chromatogram.
Being chosen as of mobile phase in described chromatographic analysis system: acetonitrile: 0.5% phosphate aqueous solution=20:80.
The extraction temperature of described coordination polymer in-line purification-accelerated solvent extraction is that 40 DEG C-90 DEG C, pressure are 1400 p.s.i.
Described chromatographic analysis system is efficient liquid phase chromatographic analysis system.
Extractant in described abstraction pool is methyl alcohol.
The mass ratio of described terephthalic acid (TPA), NaOH, nitrate trihydrate copper is 1:2:1.
The mass ratio of described sample and terephthalic acid (TPA) copper complex is 5:1 ~ 4.
The present invention compared with prior art has obvious advantage and beneficial effect, the prepared terephthalic acid (TPA) copper coordination polymer of the present invention is easy to synthesize in laboratory, material is easily obtained, this terephthalic acid (TPA) copper coordination polymer can play the basic capacity of the in-line purification sample equal with the adsorbent of existing commercialization, simultaneously than existing commercial adsorbent better effects if, it applies in the quantitative detection of microbiotic, can greatly improve experimental precision and detect accuracy, to guarantee the experiment of data and the accuracy of detection data, the method that this employing accelerated solvent extraction in-line purification method is measured antibiotic content in food or environmental sample is a kind of novel microbiotic quantitative and qualitative detection method, the method greatly reduces the interference of the detection to object, can carry out highly sensitive detection to trace materials.
figure of description
Fig. 1 is antibiotic chromatic graph spectrum in three kinds of samples in the present invention's embodiment;
Fig. 2 is the impact analysis figure that in the present invention's embodiment, coordination polymer consumption is measured microbiotic;
Fig. 3 is the comparison diagram that in the present invention's embodiment, different adsorbents are measured antibiotic content.
Embodiment
Adopt accelerated solvent extraction in-line purification method to measure a method for antibiotic content in food or environmental sample, comprise the steps,
The preparation of a, standard solution: take microbiotic standard specimen 10mg, be placed in 10ml volumetric flask, shake dissolving after adding a certain amount of solvent, carry out isochoric formation microbiotic standard specimen mother liquor with identical solvent; Microbiotic standard specimen mother liquor is adopted to the microbiotic standard solution of the method preparation variable concentrations of stepwise dilution;
The preparation of b, coordination polymer: terephthalic acid (TPA) and NaOH are added to the water, after abundant stirring and dissolving, add nitrate trihydrate copper, till being continuously stirring to and having blue powder shape precipitation generate in solution, cooling, filtration air-dry to obtain the terephthalic acid (TPA) copper complex of blue powder, be placed in brown wide-necked bottle by this blue powder for subsequent use; Prepared terephthalic acid (TPA) copper complex also claims isonicotinic acid copper (II), and the copper of this terephthalic acid (TPA) copper complex is cupric.
C, coordination polymer in-line purification-accelerated solvent extraction: sample is pulverized with comminutor, after getting a certain amount of sample and a certain amount of phthalic acid copper complex and mixing, put into the abstraction pool of accelerated solvent extraction, under the temperature and pressure condition setting, carry out auto extractive; Extractant in this abstraction pool is methyl alcohol, and this extraction temperature is that 70 DEG C, pressure are 1400 p.s.i.Liquid after extraction flows in receiving flask and collects, and this extract is passed through to constant volume at 50 DEG C of temperature, after rotary evaporation in vacuo, obtains sample extraction liquid; Certainly this extraction temperature also can be selected 40 DEG C, 50 DEG C, 60 DEG C, 65 DEG C, 80 DEG C, 90 DEG C etc., does not repeat at this.
The mensuration of d, standard solution and sample: the microbiotic standard solution that step a is prepared injects chromatographic analysis system and detects; Then the extract in step c is injected to chromatographic analysis system and detect analysis.This chromatographic analysis system is efficient liquid phase chromatographic analysis system, being chosen as of mobile phase in this chromatographic analysis system: acetonitrile: 0.5% phosphate aqueous solution=20:80.
The tetracycline that now adopts accelerated solvent extraction in-line purification method to measure in Food and environment sample is example, is specifically implemented as follows:
First, preparation tetracycline standard solution and drafting tetracycline concentration standard curve,
The preparation of tetracycline standard solution: take tetracycline standard specimen 10mg, be placed in 10ml volumetric flask, shake dissolving after adding a certain amount of solvent, carry out isochoric formation tetracycline standard specimen mother liquor with identical solvent; Tetracycline standard specimen mother liquor is adopted to the tetracycline standard solution of the method preparation variable concentrations of stepwise dilution.
The drafting of tetracycline concentration standard curve: adopt the tetracycline standard solution of the method preparation variable concentrations of stepwise dilution to inject chromatographic analysis system in tetracycline standard specimen mother liquor and detect analysis, in the concentration of standard solution and detected chromatogram, the peak area of tetracycline is as shown in table 1, the tetracycline typical curve equation being made by table 1 is y=0.2658x+0.0426, R
2=0.9997; Y represents tetracycline concentration, the corresponding peak area of tetracycline in x representative color spectrogram.
The typical curve of table 1 tetracycline
Then, prepare terephthalic acid (TPA) copper complex: the NaOH of the terephthalic acid (TPA) of 1mol and 2mol is added in deionized water, after abundant stirring and dissolving, add 1mol nitrate trihydrate copper, till continuous stirring 3 hours to the species precipitate that has blue powder shape in solution generates, cooling, also air-dry rear formation blue powder of filtration, be placed in brown light mouth bottle by this blue powder for subsequent use; Make terephthalic acid (TPA) copper complex.
Then, coordination polymer in-line purification-accelerated solvent extraction: adopt A-mud, B-chicken, C-cycle of sixty years meat is sample, after getting A-mud (5g) or B-chicken (5g) or C-cycle of sixty years meat (5g) and mixing with 2.0 g phthalic acid copper complex crushing, stirrings respectively, put into the 34mL abstraction pool of accelerated solvent extraction, taking methyl alcohol as extractant, be that 60 DEG C, pressure are to carry out auto extractive under the condition of 1400 p.s.i in temperature, the liquid after extraction flows in receiving flask and collects.
Finally, during the extract of collecting constant volume after 50 DEG C of rotary evaporation in vacuo is directly entered to chromatographic system to 5 ml, detect and analyze, obtain chromatogram, as shown in Figure 1, convert and obtain the peak area of tetracycline in three kinds of samples according to the chromatogram of Fig. 1, convert and obtain the content of tetracycline in three kinds of samples by tetracycline typical curve equation according to peak area, as shown in table 2:
The content of tetracycline and precision, the recovery in three kinds of samples of table 2
Application and the effect thereof of terephthalic acid (TPA) copper complex in reality detects is described in detail in detail, specific as follows:
As shown in Figure 3, for coordination polymer is investigated for the ability that purifies sample matrices: get respectively 0, 1, 2, 3, the coordination polymer of 5g waits the detection sample of homogenous quantities (quality is 5g) to form 5 parts of different testing mixtures from 5 parts respectively, after mixing, every part of potpourri packs in abstraction pool, sample introduction after accelerated solvent extraction and rotary evaporation are concentrated again, discovery adds the concentration of the tetracycline detecting after coordination polymer all than the height that does not add coordination polymer extraction, this shows that coordination polymer can adsorb the matrix compositions such as lipid effectively in sample preparation process, thereby improve the response of trace object tetracycline.But research is also found, along with the increase of the addition of terephthalic acid (TPA) copper coordination polymer, the value of detecting of tetracycline reduces on the contrary, this has shown that excessive terephthalic acid (TPA) copper coordination polymer has certain adsorptive power to target property, therefore must carry out by experiment to determine the optimal amount using, the optimum use amount of this terephthalic acid (TPA) copper coordination polymer is 2g, i.e. terephthalic acid (TPA) copper coordination polymer: detect sample=2:5.
As shown in Figure 3, other adsorbent comparison for coordination polymer and bibliographical information: that selects respectively that the bibliographical informations such as silica gel, Fo Luoli tripoli, aluminium oxide cross compares for the adsorbent of accelerated solvent in-line purification, and the consumption of silica gel, Fo Luoli tripoli, aluminium oxide is also the optimum use amount drawing through Optimal Experimental.Found that these in-line purification adsorbents are not all when adding adsorbent and directly extract sample, it is high that the response of tetracycline is wanted.In these four kinds of adsorbents, the detergent power of coordination polymer and silica gel is suitable, and the prepared terephthalic acid (TPA) copper coordination polymer of the present invention is optimum in four adsorbents, is secondly aluminium oxide and silica gel.
The prepared terephthalic acid (TPA) copper coordination polymer of the present invention is easy to synthesize in laboratory, material is easily obtained, this terephthalic acid (TPA) copper coordination polymer can play the basic capacity of the in-line purification sample equal with the adsorbent of existing commercialization, simultaneously than existing commercial adsorbent better effects if, it applies in the quantitative detection of microbiotic, can greatly improve experimental precision and detect accuracy, to guarantee the experiment of data and the accuracy of detection data, the method that this employing accelerated solvent extraction in-line purification method is measured antibiotic content in food or environmental sample is a kind of novel microbiotic quantitative and qualitative detection method, the detection method of other antibiotic detection methods and tetracycline is identical, can detect accurately other microbiotic equally, do not repeat at this.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, therefore every foundation technical spirit of the present invention is to any trickle amendment made for any of the above embodiments, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. adopt accelerated solvent extraction in-line purification method to measure a method for antibiotic content in food or environmental sample, it is characterized in that: comprise the steps,
The preparation of a, standard solution: get microbiotic standard specimen, be placed in volumetric flask, shake dissolving after adding a certain amount of solvent, carry out isochoric formation microbiotic standard specimen mother liquor with identical solvent; Microbiotic standard specimen mother liquor is adopted to the microbiotic standard solution of the method preparation variable concentrations of stepwise dilution;
The preparation of b, coordination polymer: terephthalic acid (TPA) and NaOH are added to the water, after abundant stirring and dissolving, add nitrate trihydrate copper, till being continuously stirring to and having blue powder shape precipitation generate in solution, cooling, filtration air-dry to obtain the terephthalic acid (TPA) copper complex of blue powder, be placed in brown wide-necked bottle by this blue powder for subsequent use;
C, coordination polymer in-line purification-accelerated solvent extraction: sample is pulverized with comminutor, after getting a certain amount of sample and terephthalic acid (TPA) copper complex and mixing, put into the abstraction pool of accelerated solvent extraction, under the temperature and pressure condition setting, carry out auto extractive; Liquid after extraction flows in receiving flask and collects, and this extract is passed through to constant volume at 50 DEG C of temperature, after rotary evaporation in vacuo, obtains sample extraction liquid;
The mensuration of d, standard solution and sample: the microbiotic standard solution that step a is prepared injects chromatographic analysis system and detects, and obtains microbiotic standard solution chromatogram; Then the extract in step c is injected to chromatographic analysis system and detect analysis, and convert and draw antibiotic content in sample according to the prepared standard equation of microbiotic standard solution chromatogram.
2. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: being chosen as of mobile phase in described chromatographic analysis system: acetonitrile: 0.5% phosphate aqueous solution=20:80.
3. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: the extraction temperature of described coordination polymer in-line purification-accelerated solvent extraction is that 40 DEG C-90 DEG C, pressure are 1400 p.s.i.
4. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: described chromatographic analysis system is efficient liquid phase chromatographic analysis system.
5. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: the extractant in described abstraction pool is methyl alcohol.
6. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: the mass ratio of described terephthalic acid (TPA), NaOH, nitrate trihydrate copper is 1:2:1.
7. a kind of method that adopts accelerated solvent extraction in-line purification method to measure antibiotic content in food or environmental sample according to claim 1, is characterized in that: the mass ratio of described sample and terephthalic acid (TPA) copper complex is 5:1 ~ 4.
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Cited By (2)
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| CN104698107A (en) * | 2015-03-24 | 2015-06-10 | 中国地质大学（武汉） | Pretreatment method of using accelerated solvent extraction on various antibiotics remained in soil |
| CN116144335A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Two-dimensional nanoemulsifier and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104698107A (en) * | 2015-03-24 | 2015-06-10 | 中国地质大学（武汉） | Pretreatment method of using accelerated solvent extraction on various antibiotics remained in soil |
| CN116144335A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Two-dimensional nanoemulsifier and preparation method and application thereof |
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