CN103278594B - Universal rapid detection method for micromolecule poisonous and harmful materials in powdery food - Google Patents
Universal rapid detection method for micromolecule poisonous and harmful materials in powdery food Download PDFInfo
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Abstract
The invention discloses a universal rapid detection method for micromolecule poisonous and harmful materials in powdery food. The method is characterized by comprising the following steps of performing simple and universal extraction and purification on a liquid milk sample to obtain a loading solution; preparing a mixed standard solution and making a matrix-adding standard curve; then measuring the micromolecule poisonous and harmful materials in the liquid milk by high performance liquid chromatography-triple quadrupole tandem mass spectrometry combination; and finally performing concentration calculation. The method has the advantages that the pretreatment and instrumental analysis processes have strong compatibility for compounds with different physicochemical properties; detection efficiency is high; operability is strong; detection limit can meet all subjected target objects; and detection cost is reduced.
Description
Technical field
The present invention relates to a kind of detection method of powdered food small molecular poisonous and harmful substance, especially the General rapid detection method of the correlation detection technologies such as the liquid chromatography-tandem mass spectrometry of ultramicron Small molecular poisonous and harmful substance in the dry powder-shaped food such as a kind of baby formula milk powder, milk powder, ground rice, oatmeal (as veterinary drug, environmental hormone, biotoxin, pesticide, adjuvant, illegal additive etc., molecular weight is less than 1500) or liquid chromatography-high resolution mass spectrum is related to.
Background technology
Dry powder-shaped food such as baby formula milk powder, milk powder, ground rice, oatmeal are the nutriment that consumption figure is huge.Affect its quality safety factor a lot, wherein of a great variety, distinct small organic molecule hazardous material (molecular weight is less than 2000) forms hidden danger in various degree to consumer health, comprise veterinary drug (microbiotic, antibiotic, hormone, growth accelerator, antiparasitic agent, antiphlogistic class etc.), agricultural chemical insecticide (as organic phosphates), biotoxin (as aflatoxin), illegal additive etc., these materials may in production, processing (bringing into auxiliary material), transport or storage link enter in product, these substance classes quantity are quite huge, physicochemical property differs greatly, add the albumen containing high level in powdered food, the matrix interference compositions such as fat and carbohydrates, huge challenge is brought to the quality control of the Small molecular poisonous and harmful substance of ultra micro content.
Along with mass spectrum especially LC-Tof Ms, the appearance of LC-MS/MS and development, multi-class multi-residue determination method has been had to report successively, within 2006, Yamada delivers LC-MS/MS method (the document 1:Yamada R that first section is screened 130 kinds of veterinary drugs in beef, pork and chicken simultaneously, Kozono M, Ohmori T, Morimatsu F, Kitayama M (2006) Biosci Biotechnol Biochem70:54 – 65), owing to using normal hexane layering degrease, be not suitable for low pole compound test, versatility is not strong; Ortelli etc. adopt acetonitrile to extract, after supernatant carries out ultrafiltration, UPLC-Tof Ms detects 150 kinds of veterinary drug (document 2:Ortelli D., Cognard E., Jan P.and Edder P. in milk, J.Chrom.B, 2009,877 (23): 2363-2374.), macrolides is lower than 10%, quinolones recovery scope 98-807%, Tetracyclines 141-258%, part benzene forces imidazoles higher than 436%, and the recovery is undesirable; Hans(2008) universal extracting method (Generic Extraction Method) concept is put forward, adopt UPLC-MS/MS to analyze 172 all agricultural chemicals, biotoxin, phytotoxin and veterinary drug in the matrix such as feed, milk, honey, meat simultaneously, be considered to universal detection method (document 3:Mol HG the earliest
p, Zomer P, de Rijk TC, Stolker AA, Mulder PP.Toward a generic extraction method for simultaneous determination of pesticides mycotoxins, plant toxins, and veterinary drugs in feed and food matrixes.Anal.Chem.2008,80 (24), 9450-9459.), but sample there is no through purified treatment in the method, detectability can not meet all tested objects, also easily pollutes instrument.Stolker etc. analyze 101 kinds of veterinary drugs in milk, and sample adopts acetonitrile to extract, the little column purification of Strata-X (document 4:Stolker A.A.M., Rutgers P., Oosterink E., Lasaroms J.J.P., Peters R.J.B., van Rhijn J.A., Nielen M.W.F., Anal.Bioanal.Chem., 2008,391 (6): 2309-2322.), by purification styles such as Solid-Phase Extraction, part of compounds may be lost in this process, and the pre-treatment time is longer again simultaneously.Above-mentioned bibliographical information multiclass multi-residue determination method, all has problems in versatility and clean-up effect.
At present, although the national standard that these venomous injurants are existing in China is for powdered food and industry standard detection method quantity more, but these methods are divided into multiple sample preparation methods, operation steps is too much, testing staff's distraction, not only waste time and energy, detection efficiency is low, operability is not strong, and project coverage rate is still not comprehensive, easily bring undetected risk, the cycle is long, experimental cost is high, has been difficult to the how residual efficient detection of venomous injurant in powdered food and supervision.Trace it to its cause, the pre-treatment of these methods is difficult to compatibility for the compound of different physicochemical property nothing more than, lacks versatility, is therefore difficult to significantly improve monitoring efficiency in conventional method.Therefore, in the face of the complicated various and quantity of kind is in the problem of ever-increasing organic contaminant and current detection standard method dispersion, improve detection efficiency and flux, reduce undetected and reduce analysis cost become industry development in the urgent need to.
Summary of the invention
Technical matters to be solved by this invention is to provide a kind of General rapid detection method of powdered food small molecular poisonous and harmful substance, the pre-treatment of the method and instrumental analysis process are compatible strong for the compound of different physicochemical property, detection efficiency is high, workable, detectability can meet all tested objects and reduce testing cost.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of General rapid detection method of powdered food small molecular poisonous and harmful substance, specifically comprises the following steps:
(1) sample extraction
5.00g milk powder or ground rice are added in plastic centrifuge tube, and in test tube, add 400mg solid EDTA-Na protective agent, 25mL extract acetonitrile, 20000rmp homogenate 1min, then the centrifugal 5min of 4500rmp, obtains the first supernatant; The solid residue of centrifugal gained is joined after fully mixing in 60% ethanol water of 12mL, add 15mL acetonitrile and repeat extraction 1 time, then the centrifugal 5min of 4500rmp obtains the second supernatant, the first supernatant and the second supernatant merging acetonitrile is settled to 50mL scale mark and obtains sample extracting solution;
(2) purification method
A. high levels of organic solvents precipitated carbohydrate
Sample extracting solution is placed in centrifuge tube, in the centrifugal 15min of 4500rmp, precipitated carbohydrate;
B. superfreeze purification
Centrifuge tube is placed in metal test tubes cover and puts into-40 DEG C of refrigerator 2h, then after the centrifugal 5min of 4500rmp, get 40mL(immediately and bring bottom settlings into reduce, only get top 40mL part), supernatant fast filtering is in heart bottle, and 30mL isopropyl alcohol is added in heart bottle, 40 DEG C are steamed near dry;
C. solid phase dispersion extracting and purifying (d-SPE)
Add at heart bottle the mixed extract and 2.5mL normal hexane that 5mL is mixed into by acetonitrile, second alcohol and water, then the liquid rotating in heart bottle is moved in centrifuge tube, after 40 DEG C of nitrogen blow evaporation removing normal hexane, add the amino filler (NH of 150mg
2) and 75mg N-propyl group ethylenediamine (PSA) filler in centrifuge tube, after abundant mixing, after the centrifugal 5min of 13000rmp, get 4mL supernatant in another centrifuge tube, 40 DEG C of nitrogen blow evaporation and blow to 0.8-1mL, then add the dimethyl sulfoxide (DMSO) of 0.6mL, fully after mixing, be settled to 1.5mL with water, measure by acquisition method LC Run1 pattern and LC Run2 pattern;
(3) mixed standard solution composition and the preparation of extraction standard curve
A. mixed standard solution composition: hybrid standard working solution concentration is in table 2, table 3.
B. extraction standard curve is quantitative: in 5g sample, add the above-mentioned standard solution of 0,50,100,200,400,800 μ L, process according to above-mentioned 1-2 pre-treatment step;
(4) Ultra Performance Liquid Chromatography-triple quadrupole bar tandem mass spectrum coupling measures
A. high-efficient liquid is separated
Liquid-phase condition is:
A) chromatographic column: Acquity Waters HSS-T
3, 2.1mm × 100mm, 1.8 μm;
If b) mass spectrum adopts Run1 positive ion mode to measure, so adopt mobile phase A
1: 0.1% aqueous formic acid, Mobile phase B
1: containing the methyl alcohol of 0.1% formic acid; Gradient elution program (with volume percentage) is: 0-7min, 100%A
1; 7-10.5min, 0%A
1; 10.5-12min, 100%A
1; Each elution time Duan Zhongjun is with Mobile phase B
1supply remaining percentage;
If mass spectrum adopt Run2 negative ions switch mode (waters instrument positive ion mode and negative ion mode can together with do, switching time 20ms) measure, so adopt mobile phase A
2: 2mmol/L ammonium acetate solution, Mobile phase B
2: methyl alcohol; Gradient elution program (with volume percentage) is: 0-7min, 100%A
2; 7-10.5min, 0%A
2; 10.5-12min, 100%A
2; Each elution time Duan Zhongjun is with Mobile phase B
2supply remaining percentage;
C) flow velocity: 0.4mL/min;
D) chromatogram column temperature: 45 DEG C;
E) sample size: 10 μ L;
F) stream switches: 0 ~ 1.5min transfer valve is opened, and column effluent enters waste liquid, starts mass spectrum collection after 1.5min, and after the whole wash-out of target analytes, flow switch is to waste liquid;
B. Mass Spectrometer Method
Mass Spectrometry Conditions is:
A) electro-spray ionization ionization source is adopted, capillary voltage: positive ion, negative ion voltage are respectively 3.5kV and 3.0kV;
B) desolventizing temperature degree: 500 DEG C, ion source temperature: 150 DEG C;
C) desolventizing flow velocity: 900L/h, taper hole flow velocity: 50L/h;
D) collision gas: argon gas 3.3 × 10
-3millibar;
E) grouping scheme: powdered food small molecular poisonous and harmful substance detects by mode shown in table 2 and 3;
(4) density calculating method
In sample, the content of determinand obtains according to following computing formula (1):
In formula:
Determinand content in X-sample, unit is that microgram often rises (μ g/L);
Testing concentration in C-sample treatment solution, calculates according to extraction standard curve, and unit is nanograms per milliliter (ng/mL);
V-constant volume, unit is milliliter (mL);
M-volume of sample, unit is milliliter (mL).
In the mixed extract described in step c of step (2), the mixed volume of acetonitrile, second alcohol and water is than being 67:10:33.
Compared with prior art, the invention has the advantages that:
1, two kinds of Extraction solvent are adopted successively to extract: first pass adopts acetonitrile homogenate to extract; After first adopting 60% ethanol water mixing for second time, then add acetonitrile solution extraction.Ensure that polarity determinand and low pole compound all obtain higher recovery simultaneously, and dry powder-shaped food can not be caused to meet water caking phenomenon; In addition, EDTA-Na
2as protective agent, prevent Tetracyclines, macrolides from being caused the recovery to reduce by metal ion-chelant;
2, high levels of organic solvents precipitated carbohydrate is effective: in extract, organic solvent concentration reaches about 92%, the water in extract, and after can adding isopropyl alcohol, rotary evaporation is near dry, realizes concentrated;
3, superfreeze method: while being reduced in of temperature does not affect the target compound recovery, the solubleness of the higher fat of content in extract, carbohydrates impurity is reduced and part is separated out, be separated by centrifugal to reach with filtration, otherwise cannot subsequent purification process be carried out;
4, dispersive solid-phase extraction (DSPE) purified treatment utilizes amino filler (NH
2) and PSA filler (150mg+75mg), solvent environment is 5mL acetonitrile+ethanol+water (67+10+33, volume ratio), the simple and efficient purification realizing sample, and the method repeatability is good.Compared with solid phase extraction, greatly improve treatment effeciency, with low cost.Utilize stream to cut, namely, 1.5min switches to waste liquid, desalination, sugar, compensate for the defect not adopting solid phase extraction column to purify.
The ratio of 5, determining organic solvent and water in solution has a significant impact testing result.This method is in order to the final constant volume of 40% dimethyl sulfoxide (DMSO) aqueous solution, can ensure that the good peak type of polar compound is with linear, can ensure again being unlikely to from determining to separate out solution and causing linearly poor phenomenon of polar compound, avoiding needs additionally to increase the requirement that LC-MS/MS analyzes number of run because determining solution different;
6, mobile phase is using methyl alcohol as organic phase, not only has price and environment-friendly advantage, and the sensitivity that most compounds obtains is higher relative to acetonitrile; Determinand is respectively using formic acid or ammonium acetate as Mobile Phase Additives, and each testing compound can realize improving chromatographic resolution and improving Ionization Efficiency flexibly.
7, this method is through the demonstration test of table 2, the concrete medicine of table 3, the average TIANZHU XINGNAO Capsul of three levels at 51.7-157.1%, its corresponding RSD(withinday precision) at 1.1-28.8% and.For second Pitch-based sphere, carried out the test of day to day precision, result shows, the RSD of the recovery is at 2.4-26.2%.Average TIANZHU XINGNAO Capsul and precision (in a few days and in the daytime) refer to form 234.For the determinand of more than 80%, the average recovery rate in milk powder and milk and repeatability are respectively between 70-120% and 1-15%, and precision is good, all can meet domestic and European Union's limitation requirement at present.This method is compared with the method for background technology Literature 2, and this method recovery is desirable, and precision is good; With the Measures compare of document 3, this method not only comprises universal extracting method, also possesses versatility purification method simultaneously, and detectability can reach 0.01 ~ 5 μ g/L; Compared with the method for document 4, rapid and simple, the recovery is high, and precision is good.
In sum, compared with above-mentioned bibliographical information multiclass multi-residue determination method, this method except detect coverage rate wider except, in the versatility of pre-treatment, clean-up effect and processing speed etc., had larger breakthrough.Extractive technique and purification techniques have versatility, detected object coverage is wide, reduce missed detection risk, the poisonous and hazardous organism of Small molecular processes by means of only a pre-treating method, add that pre-treatment is fast easy, with the detection method of multiple method in the past, detection efficiency obtains the lifting of essence, shortens sense cycle; Meanwhile, compared with employing solid phase extraction column, not only ensure the recovery of the determinand that polarity is strong and polarity is weak, and reduce the cost consumption of sample preparation.
The present invention is from the general general character of micromolecular compound, fully take into account the dissolubility of various material, thermal stability, ph stability, polarity is strong and weak, coexist stability etc., develop universal quick pretreatment technology (Generic & Rapid sample preparation), monitored by the MRM(multi-channel reaction of UPLC-ESI-MS/MS) pattern measures, under the prerequisite that satisfied detection limitation requires, can bring the effect raising the efficiency and reduce testing cost significantly to production run control and food inspection work.
Accompanying drawing explanation
Fig. 1 is the General rapid detection method process flow diagram of powdered food small molecular poisonous and harmful substance of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The invention will be further described to use embodiment below, but protection scope of the present invention is not limited to this, and protection domain is as the criterion with claim.
1, material
1.1 main agents and material
1.2 key instrument
Waters ultra high efficiency liquid phase systems (U.S. Waters, ACQUITY UPLC) and triple quadrupole bar tandem mass spectrum (U.S. Waters, XEVO TQ); Refrigerated centrifuge (German Sigma, 3-15k), Rotary Evaporators (Switzerland Buchi, Rota vapor R210) Nitrogen evaporator (U.S. OA, N-EVAP-24), Superpure water machine (French Mi Libo, Milliporeco).
2, the detection method (as shown in Figure 1) of powdered food small molecular poisonous and harmful substance
(1) sample extraction
5.00g milk powder or ground rice are added in plastic centrifuge tube, and in test tube, add 400mg solid EDTA-Na protective agent, 25mL extract acetonitrile, 20000RMP homogenate 1min, then the centrifugal 5min of 4500RMP, obtains the first supernatant; The solid residue of centrifugal gained is joined after fully mixing in 60% ethanol water of 12mL, add 15mL acetonitrile and repeat extraction 1 time, then the centrifugal 5min of 4500RMP is centrifugal obtains the second supernatant, the first supernatant and the second supernatant merging acetonitrile is settled to 50mL and obtains sample extracting solution;
(2) purification method
A. high levels of organic solvents precipitated carbohydrate
Sample extracting solution is placed in centrifuge tube, in the centrifugal 15min of 4500RMP, precipitated carbohydrate;
B. superfreeze purification
Centrifuge tube is placed in the 2h that-40 DEG C of refrigerators put into by metal test tubes cover, then after the centrifugal 5min of 4500RMP, gets 40mL supernatant liquid filtering immediately in heart bottle, and add 30mL isopropyl alcohol in heart bottle, 40 DEG C are steamed near dry;
D. solid phase dispersion extracting and purifying (d-SPE)
The mixed extract (three's volume ratio is followed successively by 67:10:33) and 2.5mL normal hexane that 5mL is mixed into by acetonitrile, second alcohol and water is added at heart bottle, then the liquid rotating in heart bottle is moved in centrifuge tube, after 40 DEG C of nitrogen blow evaporation removing normal hexane, add the amino filler (NH of 150mg
2) and 75mg PSA(N-propyl group ethylenediamine) filler is in centrifuge tube, after abundant mixing, after the centrifugal 5min of 13000RMP, get 3mL supernatant in another centrifuge tube, 40 DEG C of nitrogen blow evaporation and blow to 0.8-1mL, then add the dimethyl sulfoxide (DMSO) of 0.6mL, fully after mixing, be settled to 1.5mL with water, measure with acquisition method LC Run1 and LC Run2;
(3) mixed standard solution composition and the preparation of extraction standard curve
A. mixed standard solution composition: hybrid standard working solution concentration is in table 2, table 3.
B. extraction standard curve is quantitative: in 5g sample, add the above-mentioned standard solution of 0,50,100,200,400,800 μ L, process according to above-mentioned 1-2 pre-treatment step;
(4) Ultra Performance Liquid Chromatography-triple quadrupole bar tandem mass spectrum coupling measures
A. high-efficient liquid is separated
Liquid-phase condition is:
A) chromatographic column: Acquity Waters HSS-T
3, 2.1mm × 100mm, 1.8 μm;
If b) mass spectrum adopts Run1 pattern to measure, so adopt mobile phase A
1: 0.1% aqueous formic acid, Mobile phase B
1: containing the methyl alcohol of 0.1% formic acid; Gradient elution program (with volume percentage) is: 0-7min, 100%A
1; 7-10.5min, 0%A
1; 10.5-12min, 100%A
1; Each elution time Duan Zhongjun is with Mobile phase B
1supply remaining percentage;
If mass spectrum adopts Run2 pattern to measure, so adopt mobile phase A
2: 2mmol/L ammonium acetate solution, Mobile phase B
2: methyl alcohol; Gradient elution program (with volume percentage) is: 0-7min, 100%A
2; 7-10.5min, 0%A
2; 10.5-12min, 100%A
2; Each elution time Duan Zhongjun is with Mobile phase B
2supply remaining percentage (as shown in table 1);
The UPLC eluent gradient optimum configurations of table 1. object
C) flow velocity: 0.4mL/min;
D) chromatogram column temperature: 45 DEG C;
E) sample size: 10 μ L;
F) stream switches: 0 ~ 1.5min transfer valve is opened, column effluent enters waste liquid, starts mass spectrum collection after 1.5min;
B. Mass Spectrometer Method
Mass Spectrometry Conditions is:
A) electro-spray ionization ionization source is adopted, capillary voltage: positive ion, negative ion voltage are respectively 3.5kV and 3.0kV;
B) desolventizing temperature degree: 500 DEG C, ion source temperature: 150 DEG C;
C) desolventizing flow velocity: 900L/h, taper hole flow velocity: 50L/h;
D) collision gas: argon gas 3.3 × 10
-3millibar;
E) grouping scheme: powdered food small molecular poisonous and harmful substance detects by mode shown in table 2 and 3;
(4) density calculating method
In sample, the content of determinand obtains according to following computing formula (1):
In formula:
Determinand content in X-sample, unit is that microgram often rises (μ g/L);
Testing concentration in C-sample treatment solution, calculates according to extraction standard curve, and unit is nanograms per milliliter (ng/mL);
V-constant volume, unit is milliliter (mL);
M-volume of sample, unit is milliliter (mL).
3. demonstration test
Following form is the grouping scheme for the 300 kinds of medicines verifying the method
The compound Chinese and English title that table 2.LC Run1 gathers, chemical classification number, molecular weight, retention time, adduct ion, quota ion to, qualitative ion pair, ion ratio and standard working solution concentration
The compound Chinese and English title that table 3.LC Run2 gathers, chemical classification number, molecular weight, retention time, adduct ion, quota ion to, qualitative ion pair, ion ratio and standard working solution concentration
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned citing.Those skilled in the art are in essential scope of the present invention, and the change made, remodeling, interpolation or replacement, also should belong to protection scope of the present invention.
Claims (1)
1. a General rapid detection method for powdered food small molecular poisonous and harmful substance, is characterized in that specifically comprising the following steps:
(1) sample extraction
5.00g milk powder or ground rice are added in plastic centrifuge tube, and in test tube, add 400mg solid EDTA-Na protective agent, 25mL extract acetonitrile, 20000rmp homogenate 1min, then the centrifugal 5min of 4500rmp, obtains the first supernatant; The solid residue of centrifugal gained is joined after fully mixing in 60% ethanol water of 12mL, add 15mL acetonitrile and repeat extraction 1 time, then the centrifugal 5min of 4500rmp obtains the second supernatant, the first supernatant and the second supernatant merging acetonitrile is settled to 50mL scale mark and obtains sample extracting solution;
(2) purification method
A. high levels of organic solvents precipitated carbohydrate
Sample extracting solution is placed in centrifuge tube, in the centrifugal 15min of 4500rmp, precipitated carbohydrate;
B. superfreeze purification
Centrifuge tube is placed in metal test tubes cover and puts into-40 DEG C of refrigerator 2h, then after the centrifugal 5min of 4500rmp, get 40mL immediately, supernatant fast filtering in heart bottle, and adds 30mL isopropyl alcohol in heart bottle, and 40 DEG C are steamed near dry;
C. solid phase dispersion extracting and purifying
5mL is added by acetonitrile at heart bottle, the mixed extract that second alcohol and water is mixed into and 2.5mL normal hexane, then the liquid rotating in heart bottle is moved in centrifuge tube, after 40 DEG C of nitrogen blow evaporation removing normal hexane, add the amino filler of 150mg and 75mg N-propyl group ethylenediamine filler in centrifuge tube, after abundant mixing, after the centrifugal 5min of 13000rmp, get 4mL supernatant in another centrifuge tube, 40 DEG C of nitrogen blow evaporation and blow to 0.8-1mL, then the dimethyl sulfoxide of 0.6mL is added, after abundant mixing, 1.5mL is settled to water, measure by acquisition method LC Run 1 pattern and LC Run 2 pattern, in wherein said mixed extract, the mixed volume of acetonitrile, second alcohol and water is than being 67:10:33,
(3) mixed standard solution composition and the preparation of extraction standard curve
A. mixed standard solution composition: hybrid standard working solution concentration is in table 1, table 2;
B. extraction standard curve is quantitative: in 5g sample, add 0 μ L, 50 μ L, 100 μ L, 200 μ L, 400 μ L, the above-mentioned standard solution of 800 μ L, process according to above-mentioned (1)-(2) pre-treatment step;
(4) Ultra Performance Liquid Chromatography-triple quadrupole bar tandem mass spectrum coupling measures
A. high-efficient liquid is separated
Liquid-phase condition is:
A) chromatographic column: Acquity Waters HSS-T
3, 2.1mm × 100mm, 1.8 μm;
If b) mass spectrum adopts Run1 positive ion mode to measure, so adopt mobile phase A
1: 0.1% aqueous formic acid, Mobile phase B
1: containing the methyl alcohol of 0.1% formic acid; Gradient elution program is counted with percent by volume: 0-7min, 100%A
1; 7-10.5min, 0%A
1; 10.5-12min, 100%A
1; Each elution time Duan Zhongjun is with Mobile phase B
1supply remaining percentage;
If mass spectrum adopts Run2 to measure at negative ions switch mode, so adopt mobile phase A
2: 2mmol/L ammonium acetate solution, Mobile phase B
2: methyl alcohol; Gradient elution program is counted with percent by volume: 0-7min, 100%A
2; 7-10.5min, 0%A
2; 10.5-12min, 100%A
2; Each elution time Duan Zhongjun is with Mobile phase B
2supply remaining percentage;
C) flow velocity: 0.4mL/min;
D) chromatogram column temperature: 45 DEG C;
E) sample size: 10 μ L;
F) stream switches: 0 ~ 1.5min transfer valve is opened, and column effluent enters waste liquid, starts mass spectrum collection after 1.5min, and after the whole wash-out of target analytes, flow switch is to waste liquid;
B. Mass Spectrometer Method
Mass Spectrometry Conditions is:
A) electro-spray ionization ionization source is adopted, capillary voltage: positive ion, negative ion voltage are respectively 3.5kV and 3.0kV;
B) desolventizing temperature degree: 500 DEG C, ion source temperature: 150 DEG C;
C) desolventizing flow velocity: 900L/h, taper hole flow velocity: 50L/h;
D) collision gas: argon gas 3.3 × 10
-3millibar;
E) grouping scheme: powdered food small molecular poisonous and harmful substance detects by mode shown in table 1 and 2;
Table 1.LC Run 1 pattern
Table 2.LC Run2 pattern
(5) density calculating method
In sample, the content of determinand obtains according to following computing formula (1):
In formula:
Determinand content in X-sample, unit is that microgram often rises μ g/L;
Testing concentration in C-sample treatment solution, calculates according to extraction standard curve, and unit is nanograms per milliliter ng/mL;
V-constant volume, unit is milliliter mL;
M-volume of sample, unit is milliliter mL.
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| CN106404949A (en) * | 2016-08-31 | 2017-02-15 | 天津市中升挑战生物科技有限公司 | Detection method for content of carprofen |
| CN106840836A (en) * | 2016-12-31 | 2017-06-13 | 湖北省理化分析测试中心 | Plastic cement race track poisons detection pre-treating method |
| CN106841430A (en) * | 2017-01-04 | 2017-06-13 | 华中农业大学 | A kind of method that Liquid Chromatography-Tandem Mass Spectrometry determines anti-microbial type and forbidden drug in feed |
| CN109490451B (en) * | 2018-10-16 | 2021-08-31 | 宁波中盛产品检测有限公司 | Universal precipitation purifying agent for strong water-soluble target and pretreatment method for chromatographic and mass spectrometric detection of universal precipitation purifying agent |
| CN112198264A (en) * | 2019-07-08 | 2021-01-08 | 上海凯宝药业股份有限公司 | Method for detecting veterinary drug residues in bear gall powder |
| CN114778737B (en) * | 2022-04-27 | 2024-05-10 | 天津国科医疗科技发展有限公司 | Liquid chromatography detection sample pretreatment method capable of shortening time |
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