CN103743847A - MALDI-TOF-MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry) detection method of fluoroquinolone medicines in milk - Google Patents
MALDI-TOF-MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry) detection method of fluoroquinolone medicines in milk Download PDFInfo
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Abstract
The invention discloses an MALDI-TOF-MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry) detection method of fluoroquinolone medicines in milk. The method comprises the following steps: sieving 8-hydroxyquinoline by a functional mesoporous molecular sieve to obtain SBA (Santa Barbara Amorphous material)-15-8-hydroxyquinoline; diluting milk by trifluoroacetic acid to obtain a sample target object; dispersing the SBA-15-8-hydroxyquinoline in ethanol liquor and carrying out ultrasonic treatment to obtain suspension liquid; adding the suspension liquid into the sample target object, and naturally drying at room temperature to obtain an MALDI matrix thin layer; placing milk to be detected on the MALDI matrix thin layer, carrying out MALDI-TOF-MS analysis after a solvent is naturally evaporated, and dropping a sample and the matrix on a target plate in a mixed manner, and detecting after the target plate directly enters into the MALDI-TOF-MS, wherein a fuzzy pre-treatment process is canceled. When the residual amount of the fluoroquinolone medicines in milk exceeds 0.05mg/kg, 18 of 25 fluoroquinolone medicines in milk can be effectively detected, so that the detection efficiency is greatly improved so as to meet the demand on quick test and quick release of import and export products.
Description
Technical field
The present invention relates to the detection method of fluoroquinolones in a kind of milk, specifically, relate to the MALDI-TOF-MS detection method of fluoroquinolones in a kind of milk, belong to food safety detection technical field.
Background technology
In recent years, ground substance assistant laser absorption ionization time of flight mass spectrometry (MALDI-TOF-MS) technology is widely used in mensuration and the purity evaluation of peptide and protein molecular weight, as BCA, melittin, bovine insulin, bovine insulin B chain, gramicidin S, myoglobins, cromoci, trypsinogen etc., mensuration process is very easy, and some laboratory MALDI-TOF-MS have at home and abroad become the conventional method of protein molecule quantitative determination.Aspect polypeptide, amino acid mass spectrophotometry, mostly adopt DHB, CHCA as MALDI matrix.
At present, MALDI-TOF-MS is used for the analysis of macromolecular substances, but in the composition of actual determinand, often also include small-molecule substance, substance assistant laser desorpted ionized flight time mass spectrum (MALDI-TOF-MS) is within molecular weight is less than 400u region, due to the ionization of matrix itself, make existence in micromolecular compound mass spectrogram be difficult in a large number the assorted peak of explaining.The existence at a large amount of assorted peaks have produced very strong mass discrimination, make those not the micromolecular compound of easily ionizable be difficult to desorption ionization and go out molion.
Fluo quinolone drug residual adopts enzyme linked immunosorbent assay or Liquid Chromatography/Mass Spectrometry to detect conventionally, the pretreatment process of above detection method be in whole fluo quinolone drug residual testing process, take time and effort most, a most loaded down with trivial details link, be again the link that testing result is had the greatest impact simultaneously.At present, also do not see the research report that adopts MALDI-TOF-MS to detect fluo quinolone drug residual.
Summary of the invention
The problem to be solved in the present invention is for above deficiency, the MALDI-TOF-MS detection method of fluoroquinolones in a kind of milk is provided, and fluoroquinolones that can rapid screening Residues in Milk, adopts detection method of the present invention, pretreatment process is simple, and detection efficiency is high.
For overcoming the above problems, the technical solution used in the present invention is: the MALDI-TOF-MS detection method of fluoroquinolones in milk, is characterized in that: described detection method comprises the following steps:
The functional mesoporous molecular sieve of oxine, obtains SBA-15-8 hydroxyquinoline;
Preparation MALDI-TOF-MS sample:
Milk is diluted with trifluoroacetic acid, obtain sample object;
SBA-15-8 hydroxyquinoline is dispersed in ethanolic solution and carries out ultrasonic processing, obtain suspending liquid;
Get suspending liquid and add sample object, obtain MALDI matrix thin layer after natural drying under room temperature;
Get milk to be measured and be placed on MALDI matrix thin layer, after solvent spontaneous evaporation, carrying out MALDI-TOF-MS analysis.
A kind of prioritization scheme, described preparation MALDI-TOF-MS sample step comprises:
Get 10 μ L milk and dilute with volume ratio 1:100 0.1% trifluoroacetic acid, obtain sample object; The SBA-15-8 hydroxyquinoline of getting 1mg is dispersed in 1mL ethanolic solution and carries out ultrasonic processing, and the time is 3min, obtains suspending liquid;
Get 1 μ L suspending liquid and add sample object,, with on the milk after trifluoroacetic acid dilution, room temperature is placed 5-10min, obtains MALDI matrix thin layer after natural drying;
Measure 0.5 μ L milk to be measured and be placed on MALDI matrix thin layer, placing 5-10min, after solvent spontaneous evaporation, matrix thin layer being analyzed by MALDI-TOF-MS.
Another kind of prioritization scheme, the functional mesoporous molecular sieve step of described oxine comprises:
Mesoporous molecular sieve SBA-15 is placed in to muffle furnace baking to be dried;
Get dried mesoporous molecular sieve SBA-15 and be placed in the toluene solution that is mixed with 8 hydroxyquinolines, stir, then temperature was risen in 10 minutes to 120 ℃ and maintenance, filter again, the solid obtaining after cleaning and filtering, dry under vacuum, obtain SBA-15-8 hydroxyquinoline.
Another prioritization scheme, after MALDI-TOF-MS analyzes the mass spectrogram of milk to be measured, contrast with the mass spectrogram of plain chocolate, judge in milk to be measured, whether to contain fluorine quino ketone medicine.
The present invention adopts above technical scheme, compared with prior art, has the following advantages: sample and matrix mixing point, on target plate, are directly entered to substance assistant laser desorpted ionized flight time mass spectrum and measure, saved loaded down with trivial details pretreatment process.When fluo quinolone drug residual amount exceedes 0.05mg/kg in milk, 18 kinds in 25 kinds of fluo quinolone drug residuals can effectively be detected.The meso-porous molecular sieve material SBA-15 that utilizes oxine functionalization is matrix, the method of rapid screening is carried out in foundation to 25 kinds of fluoroquinolones in milk with MALDI-TOF-MS, can greatly improve detection efficiency, with what adapt to import and export product, test soon soon put requirement.
Below in conjunction with drawings and Examples, the invention will be further described.
Accompanying drawing explanation
Accompanying drawing 2 is for adding the MALDI mass spectrogram of concentration as the marbofloxacin of 200mg/kg take DHB as matrix in the embodiment of the present invention;
Accompanying drawing 3 is for adding the MALDI-TOF-MS mass spectrogram after QNS take CHCA as matrix in the embodiment of the present invention;
Accompanying drawing 4 is for adding the MALDI-TOF-MS mass spectrogram after QNS take SBA-15 as matrix in the embodiment of the present invention;
Accompanying drawing 5 is for adding the MALDI-TOF-MS mass spectrogram after QNS take SBA-15-8QSi as matrix in the embodiment of the present invention;
Accompanying drawing 6 adds in the embodiment of the present invention MALDI-TOF-MS mass spectrogram that concentration is the milk sample of 0.5mg/kg marbofloxacin;
Accompanying drawing 7 adds in the embodiment of the present invention MALDI-TOF-MS mass spectrogram that concentration is the milk sample of 0.05mg/kg marbofloxacin;
Accompanying drawing 8 is the partial enlarged drawing of accompanying drawing 7;
Accompanying drawing 9 adds in the embodiment of the present invention MALDI-TOF-MS mass spectrogram that concentration is the milk sample of 0.01mg/kg marbofloxacin;
Accompanying drawing 10 is the MALDI mass spectrogram take SBA-15-8QSi 25 kinds of fluoroquinolones residues of veterinary drug in matrix milk in the embodiment of the present invention.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment, the MALDI-TOF-MS detection method of fluoroquinolones in milk, comprises the following steps:
Prepare the functional mesoporous molecular sieve step of oxine:
The muffle furnace that mesoporous molecular sieve SBA-15 is placed in to 550 ℃ toasts 2 hours, and the object of heating is for removed template method;
Take 1.0g mesoporous molecular sieve SBA-15, be placed in the 10mL toluene solution that is mixed with 8 hydroxyquinolines, the content of 8QSi is 0.32g, at 80 ℃, stir 24h, then temperature was risen in 10 minutes to 120 ℃ and keep 24h, then filter, the solid obtaining after filtering is cleaned with toluene, acetone, methyl alcohol and methylene chloride successively, dry under vacuum, obtain SBA-15-8QSi, i.e. SBA-15-8 hydroxyquinoline.
Preparation MALDI-TOF-MS sample step:
Get 10 μ L milk and dilute with volume ratio 1:100 0.1% trifluoroacetic acid, obtain sample object; The SBA-15-8 hydroxyquinoline of getting 1mg is dispersed in 1mL ethanolic solution and carries out ultrasonic processing, and the time is 3min, obtains suspending liquid;
Get 1 μ L suspending liquid and add sample object,, with on the milk after trifluoroacetic acid dilution, room temperature is placed 5-10min, obtains MALDI matrix thin layer after natural drying;
Measure 0.5 μ L milk to be measured and be placed on MALDI matrix thin layer, placing 5-10min, after solvent spontaneous evaporation, the matrix thin layer containing milk sample to be measured being analyzed by MALDI-TOF-MS;
According to the working specification of MALDI-TOF-MS, carry out, obtain the mass spectrogram of milk to be measured, contrast with the mass spectrogram of plain chocolate, judge in milk to be measured, whether to contain fluorine quino ketone medicine.
Test
1, the MALDI mass spectrogram aligned protein spectrum library of the MALDI-TOF-MS mass spectrum milk sample of plain chocolate sample is known, main matter between 300-600 molecular weight area is the fragment of some peptide molecules, and the material that molecular weight is m/z8002.9 may be peptone p.p.81, and molecular ion peak may be respectively γ 3 and γ 2 caseins at the material of m/z11553.8 and 11813.8.In the molecular ion peak region of lactalbumin, be generally m/z14000 between m/z19000, have an obvious characteristic peak, m/z14154.1, it has represented lactoalbumin.From the full spectrogram (m/z300-30000) of milk sample, in discovery and this research, 25 kinds of fluoroquinolones have the molecular ion peak matching to occur, and in the interval of m/z5000-30000 can observe milk peptone, casein, lactalbumin and caseic feature molecular ion peak, plain chocolate sample does not affect test specimen.
2, DHB and CHCA add the MALDI-TOF-MS mass spectrophotometry test after QNS as matrix: the impact that this Experimental Comparison DHB and CHCA analyze for QNS in milk.
Take DHB and CHCA as matrix, in milk sample, add the marbofloxacin that concentration is 200mg/kg (m/z362.35) respectively, obtain MALDI mass spectrogram, wherein shown in Fig. 1 take CHCA as matrix, shown in Fig. 2 take DHB as matrix.
Under CHCA matrix, go out under peak situation and DHB matrix and be more or less the same, but under CHCA matrix, background interference is little a lot.The MALDI collection of illustrative plates that contrasts the milk that does not add marbofloxacin is known, in the interval of m/z300-600, has occurred the molecular ion peak of m/z361.9, matches with the molecular weight of marbofloxacin m/z362.35.Test findings shows that concentration is that the marbofloxacin milk soln of 200mg/kg can be used detecting of MALDI-TOF-MS simple and fast, meanwhile, marbofloxacin not with milk in albumen or amino acid produce specificity and interact.
3, with SBA-15, SBA-15-8QSi and CHCA are that matrix is added MALDI-TOF-MS mass spectrophotometry after QNS with SBA-15, SBA-15-8QSi and CHCA are matrix, by matrix point on target plate, natural drying rear upper machine testing, obtain the mass spectrogram under MALDI-TOF-MS, obtain the MALDI mass spectrogram under different substrates, shown in Fig. 3 take CHCA as matrix, shown in Fig. 4 take SBA-15 as matrix, shown in Fig. 5 take SBA-15-8QSi as matrix, although there is more quasi-molecular ions during take CHCA as matrix, for example m/z189 and 172, these may be to come from CHCA itself.
Compared with CHCA, SBA-15, SBA-15-8QSi substantially seldom have powerful connections peak occur.This just illustrates and adopts meso-porous molecular sieve material can weaken significantly background interference as matrix, is conducive to improve detection sensitivity.
Compared with SBA-15, SBA-15-8QSi meso-porous molecular sieve material has stronger desorb/rate of ionization, as shown in Figure 4, Figure 5.Fig. 5 is compared with Fig. 4, and molecular ion peak has higher signal intensity.This may be because more easily absorb energy after mesoporous adsorption 8QSi group.
4, take the MALDI mass spectrophotometry of SBA-15-8QSi fluoquinolone in matrix research milk
4.1 sensitivity test
In order to verify the sensitivity of MALDI Mass Spectrometer Method of fluoquinolone in the milk take SBA-15-8QSi as matrix, test design a concentration gradient, the marbofloxacin that is 100mg/kg, 50mg/kg, 10mg/kg, 5mg/kg, 0.5mg/kg, 0.05mg/kg and 0.01mg/kg according to addition respectively adds milk, and take SBA-15-8QSi as matrix, use the bombardment of 337-nm nitrogen laser, detect its detectability with MALDI-TOF-MS.Addition be greater than 0.5mg/kg produce MALDI-TOF-MS mass spectrogram similar, express no longer one by one, the MALDI-TOF-MS mass spectrogram of the following concentration of 0.5mg/kg is as shown in Fig. 6-8.
Fig. 6 is that interpolation concentration is the MALDI-TOF-MS mass spectrogram of the milk sample of 0.5mg/kg marbofloxacin, can see clearly the feature molecular ion peak of m/z 362.17.
Fig. 7 adds the MALDI-TOF-MS mass spectrogram that concentration is the milk sample of 0.05mg/kg marbofloxacin, and significantly reducing appears in the feature molecular ion peak of m/z 362.2, needs to amplify and judges, accompanying drawing 8 is amplifications of m/z363-372 part.
It is the feature molecular ion peak that the MALDI-TOF-MS mass spectrogram (m/z353-373) of the milk sample of 0.01mg/kg marbofloxacin cannot detect m/z362.2 that Fig. 9 adds concentration.That is to say the marbofloxacin that 0.05mg/kg in milk can be detected with MALDI-TOF-MS.
4.2 specificity tests
As seen from Figure 7, m/z 362.4069, the most approaching with marbofloxacin m/z 362.35, but occur in its vicinity two peaks, m/z 362.2363 and m/z 362.6433, illustrate when marbofloxacin interpolation concentration is 0.05mg/kg, exist and disturb, there will be certain false positive.
4.3 add the 25 kind fluorine quino ketone medicines of concentration as 0.05mg/kg take the MALDI mass spectrum of SBA-15-8QSi 25 kinds of fluoroquinolones residues of veterinary drug in matrix research milk simultaneously, and take SBA-15-8QSi as matrix, use the bombardment of 337nm nitrogen laser, see Figure 10 with the spectrogram that MALDI-TOF-MS detects.
The molecular ion peak of each compound is as follows: Ciprofloxacin m/z 331.35, Dan Nuosha star m/z 453.5, Enrofloxacin m/z 359.40, sarafloxacin m/z 385.36, Norfloxacin m/z 409.41, Difloxacin m/z 435.86, marbofloxacin m/z 362.35, oxolinic acid m/z 261.23, acidum nalidixicum m/z 232.24, Pefloxacin m/z 429.47, Sparfloxacin m/z 392.41, Orbifloxacin m/z 395.38, fleraxacin m/z 369.34, Lomefloxacin m/z 387.81, flumequine m/z 261.25, Enoxacin m/z 320.32, gatifloxacin m/z 375.40, Pazufloxacin m/z 318.29, MOXIFLOXACIN m/z 401.43, Nadifloxacin m/z 360.38, Danofloxacin m/z 357.38, lavo-ofloxacin m/z 370.38, pipemidic acid m/z 303.33, tosufloxacin m/z 576.54, Balofloxacin m/z 389.42.Wherein can correspondence find acidum nalidixicum m/z 232.24, pipemidic acid m/z 303.33, Enoxacin m/z 320.32, Ciprofloxacin m/z 331.35, Danofloxacin m/z 357.38, Enrofloxacin m/z 359.40, marbofloxacin m/z 362.35, lavo-ofloxacin m/z 370.38, gatifloxacin m/z 375.40, sarafloxacin m/z 385.36, Lomefloxacin m/z 387.81, Sparfloxacin m/z 392.41, MOXIFLOXACIN m/z 401.43, Norfloxacin m/z 409.41, Pefloxacin m/z 429.47, Difloxacin m/z 435.86, Dan Nuosha star m/z 453.5, totally 18 kinds of tosufloxacin m/z 576.54.
4.4 repeatability are measured
This test carried out in a few days and in the daytime repeatability mensuration.
In a few days repeatability is measured: according to detecting 18 kinds of positive fluoroquinolones milk samples in test 4.3, getting respectively its concentration is 100mg/kg, 50mg/kg, the milk sample of the same race of 0.05mg/kg, at same in a few days different time, with the sample of 6 high, medium and low 3 kinds of drug concentrations of replication of same MALDI-TOF-MS, try to achieve in a few days (in batch) repeatability.Near being determined at m/z separately, occur a molecular ion peak the highest, and every kind of each m/z difference of measuring of medicine is between 0.1-0.5 at every turn.There are two close molecular ion peaks in indivedual medicines, can be judged as false positive and exist near m/z separately.
Day to day precision is measured: getting concentration is 100mg/kg, 50mg/kg, in the 2.4.3 of 0.05mg/kg, detect 18 kinds of positive fluoroquinolones, in one week in different three days, add to respectively in three kinds of different brands milk, with the milk sample of 6 high, medium and low 3 kinds of drug concentrations of replication of same MALDI-TOF-MS, try to achieve in the daytime (between batch) repeatability.Near being determined at m/z separately, occur a molecular ion peak the highest, and every kind of each m/z difference of measuring of medicine is between 0.1-0.5 at every turn.There are two close molecular ion peaks in indivedual medicines, can be judged as false positive and exist near m/z separately.And the milk of different brands is little on result impact.
By replica test, with MALDI-TOF-MS, detect 18 kinds of fluoroquinolones in 4.3, all detect, without false negative phenomenon.
conclusion
The application MALDI-TOF-MS of this success of the test has detected that the concentration of adding in milk is 18 kinds of fluorine quinolone compounds such as 0.05mg/kg marbofloxacin, Enoxacin, this 18 kinds of medicines have been contained conventional clinically fluoroquinolones substantially, and screening concentration meets the regulation of different importers to QNS maximum residue limit(MRL) standard in milk substantially.Although the method has certain false positive near lower bound, as a kind of rapid screening method, analyze fluo quinolone drug residual in milk, whole analytic process does not need traditional complicated pretreatment process, time saving and energy saving, can greatly improve analysis efficiency.For recall rate extremely low in routine testing, after detecting, use additive method to carry out again accurate quantitative analysis, can meet import and export inspection and quarantine and test soon soon put requirement.
Ciprofloxacin (purity 95%), single husky star of promise (purity 94%), Enrofloxacin (purity 99%), Difloxacin (purity 98.5%), marbofloxacin (purity 98.5%), oxolinic acid (purity 97.5%), acidum nalidixicum (purity 99.8%), Pefloxacin (purity 99%), Sparfloxacin (purity 99%), Orbifloxacin (purity 99.8%), Lomefloxacin (purity 97.6%), flumequine (purity 98%), Enoxacin (purity 99%), Danofloxacin (purity 94%) (from Dr Ehrenstorfer company), Norfloxacin (purity 98%), sarafloxacin (purity 97%), Pazufloxacin Mesilate (purity 75.3%), lavo-ofloxacin (purity 98%), pipemidic acid (purity 99%) (from Sigma company), MOXIFLOXACIN (purity 99%), fleraxacin (purity 99.1%), gatifloxacin (purity 98%), Nadifloxacin (purity 92%), tosufloxacin (purity 98.9%), Balofloxacin (purity 99.5%) (China Veterinary Drugs Supervisory Inst.'s friendship provides), trifluoroacetic acid (TFA), 2,5-dihydroxy-benzoic acid (DHB) and alpha-cyano-4-hydroxycinnamic acid (CHCA) (analyze pure, Fluka (St.Louis, MO) company), toluene, acetone, absolute ethyl alcohol, methylene chloride (chromatographically pure, Tianjin Ke Miou), methyl alcohol (chromatographically pure, Fisher), 8-(3-(triethoxy) propoxyl group) quinoline (8QSi), mesopore molecular sieve (the friendship patronage of Changchun applied chemistry study institute), plain chocolate (Erie, Mongolia Ox, bright brand, Tesco).Water (secondary water, laboratory self-control).
Instrument and equipment
AXIMA-TOF2 type MALDI-TOF mass spectrometer: Japanese Shimadzu company product, nitrogen laser, wavelength 337nm, adopts delayed ion extraction and reflecting operating mode.
Unless stated otherwise, the degree relating to is mass percentage content.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. the MALDI-TOF-MS detection method of fluoroquinolones in milk, is characterized in that: described detection method comprises the following steps:
The functional mesoporous molecular sieve of oxine, obtains SBA-15-8 hydroxyquinoline;
Preparation MALDI-TOF-MS sample:
Milk is diluted with trifluoroacetic acid, obtain sample object;
SBA-15-8 hydroxyquinoline is dispersed in ethanolic solution and carries out ultrasonic processing, obtain suspending liquid;
Get suspending liquid and add sample object, obtain MALDI matrix thin layer after natural drying under room temperature;
Get milk to be measured and be placed on MALDI matrix thin layer, after solvent spontaneous evaporation, carrying out MALDI-TOF-MS analysis.
2. the MALDI-TOF-MS detection method of fluoroquinolones in milk as claimed in claim 1, is characterized in that: described preparation MALDI-TOF-MS sample step comprises:
Get 10 μ L milk and dilute with volume ratio 1:100 0.1% trifluoroacetic acid, obtain sample object; The SBA-15-8 hydroxyquinoline of getting 1mg is dispersed in 1mL ethanolic solution and carries out ultrasonic processing, and the time is 3min, obtains suspending liquid;
Get 1 μ L suspending liquid and add sample object,, with on the milk after trifluoroacetic acid dilution, room temperature is placed 5-10min, obtains MALDI matrix thin layer after natural drying;
Measure 0.5 μ L milk to be measured and be placed on MALDI matrix thin layer, placing 5-10min, after solvent spontaneous evaporation, matrix thin layer being analyzed by MALDI-TOF-MS.
3. the MALDI-TOF-MS detection method of fluoroquinolones in milk as claimed in claim 1 or 2, is characterized in that: the functional mesoporous molecular sieve step of described oxine comprises:
Mesoporous molecular sieve SBA-15 is placed in to muffle furnace baking to be dried;
Get dried mesoporous molecular sieve SBA-15 and be placed in the toluene solution that is mixed with 8 hydroxyquinolines, stir, then temperature was risen in 10 minutes to 120 ℃ and maintenance, filter again, the solid obtaining after cleaning and filtering, dry under vacuum, obtain SBA-15-8 hydroxyquinoline.
4. the MALDI-TOF-MS detection method of fluoroquinolones in milk as claimed in claim 1, it is characterized in that: the mass spectrogram that obtains milk to be measured after MALDI-TOF-MS analyzes, contrast with the mass spectrogram of plain chocolate, judge in milk to be measured, whether to contain fluorine quino ketone medicine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203623A (en) * | 2015-08-31 | 2015-12-30 | 陕西师范大学 | Application of 6-tertiary butyl-6-hexyloxy-6-benzo[a,b,de,lm,op,rs,uv]coronene as MALDI-TOF MS matrix in micromolecule detection |
| CN106841423A (en) * | 2016-12-30 | 2017-06-13 | 广州中大南沙科技创新产业园有限公司 | A kind of UHPLC MS/MS analysis methods of measure 83b1 PCs |
| CN108051512A (en) * | 2017-11-27 | 2018-05-18 | 佛山科学技术学院 | The detection method of fluo quinolone drug residual amount in a kind of cow's milk |
| CN108219777A (en) * | 2018-03-03 | 2018-06-29 | 郭迎庆 | A kind of preparation method of high fluorescent high temperature resistant fluorescent material |
| CN109187717A (en) * | 2018-09-27 | 2019-01-11 | 中国科学技术大学 | The detection method of external source organic pollutant in a kind of plant |
| CN113861074A (en) * | 2021-09-23 | 2021-12-31 | 中国检验检疫科学研究院 | Preparation method and application of novel ionic liquid MALDI matrix |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560625A (en) * | 2004-03-11 | 2005-01-05 | 复旦大学 | Trace polypeptide or protein-enriched and its direct analyzing method |
| JP2009098108A (en) * | 2007-10-18 | 2009-05-07 | Bio Matrix Research Inc | Refinement method of material having sugar chain and utilization of the same |
| JP2010044064A (en) * | 2008-07-18 | 2010-02-25 | Shizuoka Prefecture | Protein profiling method by 2d-lcms/ms total spectra |
| CN102253110A (en) * | 2011-06-09 | 2011-11-23 | 曹际娟 | Method for auxiliary identification of comma bacillus by matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry (MALDI-TOF MS) |
-
2013
- 2013-12-31 CN CN201310746995.1A patent/CN103743847A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560625A (en) * | 2004-03-11 | 2005-01-05 | 复旦大学 | Trace polypeptide or protein-enriched and its direct analyzing method |
| JP2009098108A (en) * | 2007-10-18 | 2009-05-07 | Bio Matrix Research Inc | Refinement method of material having sugar chain and utilization of the same |
| JP2010044064A (en) * | 2008-07-18 | 2010-02-25 | Shizuoka Prefecture | Protein profiling method by 2d-lcms/ms total spectra |
| CN102253110A (en) * | 2011-06-09 | 2011-11-23 | 曹际娟 | Method for auxiliary identification of comma bacillus by matrix-assisted laser desorption ionisation-time-of-flight mass spectrometry (MALDI-TOF MS) |
Non-Patent Citations (1)
| Title |
|---|
| 张金玲等: "MALDI-TOF-MS技术筛选牛奶中氟喹诺酮类药物", 《食品研究与开发》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203623A (en) * | 2015-08-31 | 2015-12-30 | 陕西师范大学 | Application of 6-tertiary butyl-6-hexyloxy-6-benzo[a,b,de,lm,op,rs,uv]coronene as MALDI-TOF MS matrix in micromolecule detection |
| CN106841423A (en) * | 2016-12-30 | 2017-06-13 | 广州中大南沙科技创新产业园有限公司 | A kind of UHPLC MS/MS analysis methods of measure 83b1 PCs |
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| CN108219777A (en) * | 2018-03-03 | 2018-06-29 | 郭迎庆 | A kind of preparation method of high fluorescent high temperature resistant fluorescent material |
| CN109187717A (en) * | 2018-09-27 | 2019-01-11 | 中国科学技术大学 | The detection method of external source organic pollutant in a kind of plant |
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