CN104897767B - Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning - Google Patents
Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning Download PDFInfo
- Publication number
- CN104897767B CN104897767B CN201510262973.7A CN201510262973A CN104897767B CN 104897767 B CN104897767 B CN 104897767B CN 201510262973 A CN201510262973 A CN 201510262973A CN 104897767 B CN104897767 B CN 104897767B
- Authority
- CN
- China
- Prior art keywords
- honey
- ion
- chlopyrifos
- mark
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to detection technique field, discloses the method that neutral desorption-electron spray extraction MALDI-MS directly detects the dead tick of honey poisoning, includes the preparation of (1) mark-on honey；(2) neutral desorption-electron spray extraction MALDI-MS detection chlopyrifos extractant and the selection of neutral strippant；(3) m/z 352 three-level fragments characteristic ion m/z 296 is selected to carry out the amount that quantitative analysis draws the dead tick of honey poisoning.The present invention realizes the quick detection to the dead tick of honey poisoning and identification, improves the defects of existing analytical technology operating procedure is complicated, time-consuming without being pre-processed to testing sample.
Description
Technical field
The invention belongs to the detection method of detection technique field, the more particularly to dead tick of honey poisoning.
Background technology
Chlopyrifos is a kind of widely used high-efficiency broad spectrum organophosphorus pesticide, both can do hygienic deinsectization medicine again with mite killing,
It is mainly used in the prevention and control of plant diseases, pest control of the various crops such as vegetables fruit tree, cotton, but the threat to nectariferous plant is larger.Toxicologic study
Show, chlopyrifos has the function that to significantly inhibit cholinesterase activity, produces murder by poisoning to the central nervous system of mouse, and have
Certain teratogenesis.The analysis and research of organophosphorus pesticide show in honey, and residual of the chlopyrifos in honey is exceeded existing
As generally existing.China is the first in the world bee-keeping big country, and bee product produces and big export country.With living standards of the people
Improve and the fast development of foreign trade, the chlopyrifos residue in honey, which has become, influences the primary of China's honey outlet
Factor, seriously endanger national food security and expanding economy.
At present, conventional chlopyrifos detection method have enzyme-linked immunosorbent assay, high performance liquid chromatography, Liquid Chromatography/Mass Spectrometry,
Gas chromatography mass spectrometry method etc..These methods are typically necessary the sample pretreatment process of complexity, have complex for operation step, time-consuming etc. lack
Fall into, the detection band to the dead tick of honey poisoning carrys out many inconvenience.
The content of the invention
It is an object of the invention to provide a kind of new method directly detected to honey poisoning dead tick residual.The present invention is in nothing
Under conditions of needing sample pretreatment, the chlopyrifos in honey is directly used for quickly detecting.The present invention uses the three-level of chlopyrifos
Fragment of connecting carries out quantitative analysis, avoids false positive, improves the accuracy of detection.
Detection method of the present invention is the LTQ-XL Linears ion trap mass spectrometer and neutral desorption-electricity by routine
Spray extraction ionizes (neutral desorption-extractive electrospray ionization mass
Spectrometry, ND-EESI) source carry out containing chlopyrifos honey sample detection.
Technical solution of the present invention is as follows：
The method that a kind of neutral desorption-electron spray extraction MALDI-MS directly detects the dead tick of honey poisoning, including following step
Suddenly：
(1) mark-on honey is prepared：Testing sample honey is weighed, it is stand-by；
Mark-on honey is prepared：Parallel several parts weigh with the weight such as testing sample honey without chlopyrifos honey, are separately added into ladder
The chlopyrifos solution of concentration is spent, is stirred, it is stand-by into mark-on honey；
Testing sample honey and mark-on honey are sealed into 65 DEG C of water-bath 5min with preservative film；Treat that honey is cooled to room temperature,
Detected；
(2) neutral desorption-electron spray extraction MALDI-MS detection：ND-EESI-MS is arranged to positive ion detection pattern,
Mass Spectrometer Method scanning range is m/z 50~400；Reagent is desorbed by neutrality of methanol aqueous solution；Ionization voltage 3.5kV；Ion passes
Defeated pipe temperature is 300 DEG C；Atomization gas is nitrogen, pressure 1.0MPa；Extractant formic acid：Methanol：Water volume ratio 1:2:2, flow velocity
For 4 μ L/min；
When collision induced dissociation is tested, the width of chlopyrifos parent ion m/z 352 is arranged to 1.2Da, collision energy 30%, touches
It is 30ms to hit the duration；The ion widths of two level m/z 324 are arranged to 1.4Da, collision energy 15%, and collision duration is
30ms, quota ion is used as using three-level m/z 296；
Other parameters use LTQ-MS system Automatic Optimals；Spraying solvent channel is 30 ° with horizontal plane angle, solvent spray
Mouth is 0.5cm with mass spectrum mouth distance；To ensure that sample molecule is collided and reacted with reagent ion to greatest extent, two sprays
Mist passage angle α is kept for 60 °, and sample nozzle and mass spectrum entrance distance d are 0.5cm, and β angles are as shown in Figure 1；
(3) whether the judgement containing chlopyrifos：If there is the ion signal peaks of m/z 296 in m/z 352 three-level fragment,
Illustrate there is chlopyrifos in sample；
M/z 352 three-level fragments characteristic ion m/z 296 is selected to carry out quantitative analysis, it is dense with the dead tick of mark-on honey poisoning
Spend for abscissa, draw standard curve by ordinate of m/z 296 absolute signal strengths, drawn according to standard curve and treat test sample
The concentration of the dead tick of product honey poisoning.
The beneficial effects of the invention are as follows:(1) detection limit is lower, and the detection to the dead tick of honey poisoning is limited to 1.64ng/mL.
(2) false positive is avoided as quantifiable signal using three-level signal.(3) the inventive method uses formic acid：Methanol：Water (1:2:2)
Spraying carries out neutral desorption, and desorption efficiency is high, improves the intensity of echo signal.(4) in-situ study of honey is realized, without
Sample is pre-processed.(5) make it possible the application of the directly quick honey pollutant monitoring technology of realization, produced for honey
The sustainable development of industry lays the foundation.
Brief description of the drawings
Fig. 1 is the ND-EESI Experimental equipments of the inventive method.
Fig. 2 is the MS of chlopyrifos of the present invention (100ng/mL)nSpectrogram, in figure, (a) is chlopyrifos methanol solution first mass spectrometric
Figure, (b) is chlopyrifos methanol solution tandem mass spectrum figure, and (c) is mark-on honey chlopyrifos first mass spectrometric figure, and (d) is mark-on honey
Chlopyrifos tandem mass spectrum figure.
Fig. 3 becomes for m/z 296CID signal intensities in present invention spraying reagent Optimal Experimental with the change of electron spray extractant
Gesture figure, (1) is that different organic solvents are used as extractant in figure, and (2) are various concentrations formic acid methanol solution as extractant, (3)
A-D is respectively the methanol of 20% formic acid+80%；The acetone of+40% methanol of 20% formic acid+40%；The methanol+40% of 20% formic acid+40%
Ethyl acetate；The water of+40% methanol of 20% formic acid+40%.
Fig. 4 is the signal strength maps of m/z 296 under the different neutral strippants of the present invention.
Fig. 5 is the optimization figure that chlopyrifos mass spectrum behavior condition is influenceed in the present invention, and in figure, (a) is the excellent of electron spray voltage
Change figure, (b) is the optimization figure of extractant flow velocity, and (c) is the optimization figure of atomization gas pressure, and (d) is the optimization figure of desorption air pressure,
(e) it is the optimization figure of ion transfer tube temperature.
Fig. 6 is the working curve of various concentrations mark-on honey.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
The mass spectrograph that example of the present invention uses is the XL Linear ion trap matter of LTQ mono- of Finnigan companies of the U.S.
Spectrometer, data handling system are the XCalibur data handling systems of Finnigan companies of the U.S..
Neutral desorption apparatus and EESI ion gun, voluntarily developed with instrument key lab by Jiangxi Province's mass spectrum science；Essence
Close electronic balance (METTLERTOLEDO).Methanol (chromatographically pure, SKCHEM works are with LS)；Chlopyrifos standard items (purity 99%,
Aladdin Reagent Company)；The mass spectrograph that example of the present invention uses is the LTQ-XL Linears of Finnigan companies of the U.S.
Ion trap mass spectrometer, data handling system are the Xcalibur data handling systems of Finnigan companies of the U.S..
Embodiment 1
This experiment is tested using the ND-EESI-MS methods shown in Fig. 1 to chlopyrifos honey solution (100ng/mL),
(1) chlopyrifos standard liquid：The appropriate chlopyrifos standard items of precise, in methyl alcohol, being made into concentration is for dissolving
2mg/mL chlopyrifos standard liquid, is kept in dark place in -3 DEG C.100 μ L 2mg/mL chlopyrifos standard liquids are taken, it is dilute with ultra-pure water
Release to 4mL, concentration is 50 μ g/mL.
(2) mark-on honey chlopyrifos solution：Graduated cylinder is placed in assay balance, peeling zero, 9.9mL honeybees is taken with graduated cylinder correct amount
Honey, weigh, be 13.96232g.Each 10mL conical flasks are then placed in assay balance respectively, peeling zero, weighed respectively
13.96g honey.65 DEG C of water-bath 5min are sealed with preservative film after weighing, measure the μ g/mL dilutions of 100 μ L 50 in respectively filling honey
Conical flask in, stir.Treat that honey is cooled to room temperature, carry out Mass Spectrometer Method.
As a result as shown in Fig. 2 chlopyrifos is under ND-EESI ion guns, positive ion mode, m/z352 chlopyrifos
[C9H11Cl3NO3PS]+During Tandem Mass Spectrometry Analysis, fragment ion has m/z324, m/z 296, m/z 278.They are respectively m/z
352 lose 1 (- C2H5), 2 (- C2H5), 2 (- C2H5) and an one's share of expenses for a joint undertaking H2O.Again to m/z 324, m/z296 is CID, enters one
Step confirms above scission fragments, consistent with the fragments characteristic in document.To ensure experimental reliability, using EESI-MS pairs
100ng/mL chlopyrifos standard liquid has carried out MS/MS mass spectrum check analysis, the results showed that, chlopyrifos ND-EESI-MSnSpectrogram
With its EESI-MSnSpectrogram fits like a glove.Therefore, if signal peak m/z352 can be detected in actual sample, and in MS/MS
Principal character ion m/z 324 and m/z296 is observed in spectrogram, then may determine that in the sample and contain chlopyrifos.
To exclude false positive when detecting, three-level fragments characteristic quasi-molecular ions m/z296 is used as echo signal, to improve it
Signal intensity, this experiment has carried out the optimization of spraying reagent, using 100ng/mL chlopyrifos mark-on honey as experimental subjects, with three
Level mass signal m/z296 response intensity is standard, enters water-filling, methanol, ethanol, ethyl acetate, propyl alcohol, butanol, benzene and to two
The Optimal Experimental of toluene, acetonitrile and acetone, as shown in Fig. 3 (1).By largely groping, using the first of different formic acid volume fractions
Alcohol finds that acid adding has extraordinary effect, as a result as chlopyrifos three-level characteristic ion m/z296 signal intensities under extractant
As shown in Fig. 3 (2), 20% formic acid methanol solution is shown in as spraying reagent, the three-level fragments characteristic m/ of the dead tick of honey poisoning
Z296 signal intensities are most strong, but the maximum acid concentration that mass spectrometer can allow is 20%, can not increase acid concentration again for this.To visit
Rope is preferably sprayed reagent, using the methanol of 20% formic acid+80%；The acetone of+40% methanol of 20% formic acid+40%；20% formic acid+
The ethyl acetate of 40% methanol+40%；As a result the water of+40% methanol of 20% formic acid+40% is shown, 20% first as electron spray reagent
The sour water effect of+40% methanol+40% is best, such as Fig. 3 (3).Therefore, the extractant of this experiment be the methanol of 20% formic acid+40%+
40% water mixed solution.
This experiment has carried out neutral strippant and explored, using the water of+40% methanol of 20% formic acid+40% as electron spray extractant,
Successively by the water of 90% methanol+10%, the water of 80% methanol+20%, the water of 60% methanol+40%, the water of 40% methanol+60%, 20% first
The water of alcohol+80%, 100% water are that strippant detects the signal intensities of chlopyrifos thtee-stage shiplock characterising mass spectrometry fragment m/z 296, as a result such as
Shown in Fig. 4.
This experiment has carried out the exploration of ion gun condition, according to the mass spectrum behavior of chlopyrifos standard liquid, in cation mould
Under formula, chlopyrifos thtee-stage shiplock characterising mass spectrometry fragment m/z 296 mass spectrum response signal intensity is selected to represent to chlopyrifos
The detection efficiency of molecule.As shown in Fig. 5 (a), during voltage too small (being less than 1.5kV), signal intensity is relatively low, with the increasing of voltage
Height, Target Signal Strength raise rapidly, and when voltage too big (being more than 3.5kV), signal intensity decreases on the contrary, in 3.5kV
When reach optimal；As shown in Fig. 5 (b), extraction efficiency of the electron spray solvent flow rate in 4 μ L/min is maximum；As shown in Fig. 5 (c),
Experiment shows, with the increase of atomization pressure, Target Signal Strength also increases therewith, when air pressure (is more than more than certain value
When 1.0MPa), most of ion can be buried in oblivion also can significantly decline in mass spectrum mouth edge, Target Signal Strength, be reached in 1MPa
To optimal；As shown in Fig. 5 (d), signal is most strong when desorption air pressure is 1.2MPa, desorption efficiency highest；As shown in Fig. 5 (e), temperature
After from 100 DEG C~300 DEG C, Target Signal Strength raises rapidly, but temperature is more than 300 DEG C, signal intensity gradually reduces, because
This, experimental selection ion transfer tube temperature is 300 DEG C.
Mark-on chlopyrifos experiment is carried out according to above-mentioned experimental method, to determine the range of linearity of this method and detection limit.By
Detected in real time in honey sample, in order to exclude the false positive of signal, experimental selection m/z 352 three-level fragments characteristic ion
M/z 296 carries out quantitative analysis, while deducts corresponding blank background.The standard sample of each concentration determines 6 times, with m/z
296 absolute signal strengths average value draws curve with corresponding chlopyrifos concentration, as shown in Figure 6.Experiment shows, in chlopyrifos
In the range of 100~1000ng/mL of concentration, ionic strength has preferable linear relationship, equation of linear regression y=with concentration
2.444x-63.76 R2=0.997.According to LOD=c3 σ/S, S/N=3, c are the concentration of standard items, and σ is standard deviation, and S is
Net phase induction signal average strength), calculate detection of this method to mark-on honey is limited to 1.64ng/mL.
Embodiment 2
The method that a kind of neutral desorption-electron spray extraction MALDI-MS directly detects the dead tick of honey poisoning, including following step
Suddenly：
(1) mark-on honey is prepared：Testing sample honey is weighed, it is stand-by；
Mark-on honey is prepared：Parallel several parts weigh with the weight such as testing sample honey without chlopyrifos honey, are separately added into ladder
The chlopyrifos solution of concentration is spent, is stirred, it is stand-by into mark-on honey；
Testing sample honey and mark-on honey are sealed into 65 DEG C of water-bath 5min with preservative film；Treat that honey is cooled to room temperature,
Detected；
(2) neutral desorption-electron spray extraction MALDI-MS detection：ND-EESI-MS is arranged to positive ion detection pattern,
Mass Spectrometer Method scanning range is m/z 50~400；Reagent is desorbed by neutrality of methanol aqueous solution；Ionization voltage 3.5kV；Ion passes
Defeated pipe temperature is 300 DEG C；Atomization gas is nitrogen, pressure 1.0MPa；Extractant formic acid：Methanol：Water volume ratio 1:2:2, flow velocity
For 4 μ L/min；
When collision induced dissociation is tested, the width of chlopyrifos parent ion m/z 352 is arranged to 1.2Da, collision energy 30%, touches
It is 30ms to hit the duration；The ion widths of two level m/z 324 are arranged to 1.4Da, collision energy 15%, and collision duration is
30ms, quota ion is used as using three-level m/z 296；
Other parameters use LTQ-MS system Automatic Optimals；Spraying solvent channel is 30 ° with horizontal plane angle, solvent spray
Mouth is 0.5cm with mass spectrum mouth distance；To ensure that sample molecule is collided and reacted with reagent ion to greatest extent, two sprays
Mist passage angle is kept for 60 °, and sample nozzle is 0.5cm with mass spectrum entrance distance；
(3) whether the judgement containing chlopyrifos：If there is the ion signal peaks of m/z 296 in m/z 352 three-level fragment,
Illustrate there is chlopyrifos in sample.
M/z 352 three-level fragments characteristic ion m/z 296 is selected to carry out quantitative analysis, it is dense with the dead tick of mark-on honey poisoning
Spend for abscissa, draw standard curve by ordinate of m/z 296 absolute signal strengths, drawn according to standard curve and treat test sample
The concentration of the dead tick of product honey poisoning.
Embodiment 3
(1) commercially available honey 13.96g is weighed in 10mL conical flasks, and preservative film seals 65 DEG C of water-bath 5min；Treat that honey cools down
To room temperature, detected；
(2) neutral desorption-electron spray extraction MALDI-MS detection：ND-EESI-MS is arranged to positive ion detection pattern,
Mass Spectrometer Method scanning range is m/z 50~400；With methanol：Water volume ratio 1：1 is neutral desorption spraying reagent；Ionization voltage
3.5kV；Ion transfer tube temperature is 300 DEG C；Atomization gas is nitrogen, pressure 1.0MPa；Extractant formic acid：Methanol：Water volume
Than 1:2:2, flow velocity is 4 μ L/min；
When collision induced dissociation is tested, the width of chlopyrifos parent ion m/z 352 is arranged to 1.2Da, collision energy 30%, touches
It is 30ms to hit the duration；The ion widths of two level m/z 324 are arranged to 1.4Da, collision energy 15%, and collision duration is
30ms, quota ion is used as using three-level m/z 296；
Other parameters use LTQ-MS system Automatic Optimals；Spraying solvent channel is 30 ° with horizontal plane angle, solvent spray
Mouth is 0.5cm with mass spectrum mouth distance；To ensure that sample molecule is collided and reacted with reagent ion to greatest extent, two sprays
Mist passage angle is kept for 60 °, and sample nozzle is 0.5cm with mass spectrum entrance distance；
(3) whether the judgement containing chlopyrifos：If there is the ion signal peaks of m/z 296 in m/z 352 three-level fragment,
Illustrate there is chlopyrifos.
The measure of sample Chlorpyrifos content：Gathered by the device in honey sample has in m/z 352 three-level fragment
The ion signal peaks of m/z 296, obtain its signal strength data, and the data are substituted into formula：Y=2.444x-63.76, calculate
To the content (concentration unit ng/mL) of sample Chlorpyrifos.
To 50 and 500ng/mL chlopyrifos honey solution parallel determination 6 times, calculated by standard curve, the rate of recovery is respectively
82.02% and 109.28%, precision (RSD) is respectively 4.02% and 4.34%.
Claims (2)
1. the method that a kind of neutral desorption-electron spray extraction MALDI-MS directly detects the dead tick of honey poisoning, it is characterised in that bag
Include following steps：
(1) mark-on honey is prepared：Testing sample honey is weighed, it is stand-by；
Mark-on honey is prepared：Parallel several parts weigh with the weight such as testing sample honey without chlopyrifos honey, and it is dense to be separately added into gradient
The chlopyrifos solution of degree, stirs, stand-by into mark-on honey；
Testing sample honey and mark-on honey are sealed into 65 DEG C of water-bath 5min with preservative film；Treat that honey is cooled to room temperature, carry out
Detection；
(2) neutral desorption-electron spray extraction MALDI-MS detection：ND-EESI-MS is arranged to positive ion detection pattern, mass spectrum
Detection scanning range is m/z 50~400；Reagent is desorbed by neutrality of methanol aqueous solution；Using formic acid methanol aqueous solution as electron spray
Extraction agent；Ionization voltage 3.5kV；Ion transfer tube temperature is 300 DEG C；Atomization gas is nitrogen, pressure 1.0MPa；Electron spray
Extraction agent flow velocity is 4 μ L/min；
When collision induced dissociation is tested, the width of chlopyrifos parent ion m/z 352 is arranged to 1.2Da, and collision energy 30%, collision is held
The continuous time is 30ms；The ion widths of two level m/z 324 are arranged to 1.4Da, collision energy 15%, and collision duration is
30ms, quota ion is used as using three-level m/z 296；
Other parameters use LTQ-MS system Automatic Optimals；Spray solvent channel and horizontal plane angle is 30 °, solvent spray mouth with
Mass spectrum mouth distance is 0.5cm；To ensure that sample molecule is collided and reacted with reagent ion to greatest extent, two sprayings are logical
Road angle is kept for 60 °, and sample nozzle is 0.5cm with mass spectrum entrance distance；
(3) whether the judgement containing chlopyrifos：If there are the ion signal peaks of m/z 296, explanation in m/z 352 three-level fragment
There is chlopyrifos in sample；
Select m/z 352 three-level fragments characteristic ion m/z 296 carry out quantitative analysis, using the dead tick concentration of mark-on honey poisoning as
Abscissa, standard curve is drawn by ordinate of m/z 296 absolute signal strengths, it is special according to m/z in sample 352 three-level
Sign fragment ion m/z 296 signal intensity substitutes into the concentration that calibration curve formula draws the dead tick of testing sample honey poisoning.
2. according to the method for claim 1, it is characterised in that with methanol：Water volume ratio 1：1 is neutral desorption reagent；With first
Acid：Methanol：Water volume ratio 1:2:2 be electron spray extraction agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262973.7A CN104897767B (en) | 2015-05-22 | 2015-05-22 | Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262973.7A CN104897767B (en) | 2015-05-22 | 2015-05-22 | Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104897767A CN104897767A (en) | 2015-09-09 |
| CN104897767B true CN104897767B (en) | 2017-11-21 |
Family
ID=54030564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510262973.7A Active CN104897767B (en) | 2015-05-22 | 2015-05-22 | Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104897767B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105445360A (en) * | 2015-11-30 | 2016-03-30 | 南昌大学 | Method for quickly detecting dichlorvos in honey through ND-EESI-MS (neutral desorption-extractive electrospray ionization-mass spectrography) |
| CN105571903B (en) * | 2016-02-04 | 2018-05-08 | 南昌大学第二附属医院 | A kind of neutrality solution smokes automatic sampling apparatus and ionization mass spectrometry method |
| CN105606693B (en) * | 2016-03-15 | 2018-12-04 | 南昌大学 | The method that electron spray extraction ionization mass spectrometry directly detects five kinds of chemical pollutants in propolis |
| CN106596698B (en) * | 2016-11-10 | 2019-07-26 | 南昌大学 | The method of lotus seeds new-old degree is differentiated using direct mass spectrum imaging technology |
| CN108414608B (en) * | 2018-01-23 | 2021-01-01 | 中国中医科学院中药研究所 | Method for real-time on-line monitoring and analyzing chemical components in complex reaction system and special device thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101458226B (en) * | 2008-12-29 | 2013-04-10 | 东华理工大学 | Neutral desorption apparatus and neutral desorption extractive electrospray lonization mass spectrometry method |
| CN103822964B (en) * | 2013-10-21 | 2016-02-24 | 南昌大学 | Chloromycetin in neutral desorb-electron spray extraction MALDI-MS direct-detection honey |
| CN104897782B (en) * | 2015-06-21 | 2017-06-13 | 广东华泰检测科技有限公司 | Connection in series-parallel automated ultrasonic flaw detecting and defect recheck equipment |
-
2015
- 2015-05-22 CN CN201510262973.7A patent/CN104897767B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104897767A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104897767B (en) | Neutral desorption electrospray extracts the dead tick of ionization mass spectrometry quick detection honey poisoning | |
| CN103822964B (en) | Chloromycetin in neutral desorb-electron spray extraction MALDI-MS direct-detection honey | |
| CN101113970B (en) | Mass spectra ion source without external high pressure and ionization analytical method thereof | |
| CN103808846B (en) | Series quadrupole-rod gas-chromatographic mass spectrometry detection method for 35 toxic medicaments in urine | |
| CN104991017B (en) | Liquid chromatogram-tandem mass spectrometry method for determining isothiazolinone bactericides contained in water-based adhesive | |
| CN109917028A (en) | Agricultural chemical compound electronic identity database and detection method in edible agricultural product based on LC-Q-Orbitrap | |
| CN103424489B (en) | Method for measuring diallyl phthalate migration in food contact materials | |
| CN101458226B (en) | Neutral desorption apparatus and neutral desorption extractive electrospray lonization mass spectrometry method | |
| CN105319292A (en) | UPLC-MS/MS method for analyzing four categories and 29 types of restricted veterinary drug residues in animal foodstuff | |
| CN102636581A (en) | Liquid chromatogram and fluorescence method for simultaneously detecting aflatoxin B1, ochratoxin A, zearalenone and citrinin in grains | |
| CN102280347A (en) | Normal pressure chemical extraction ionization source and normal pressure extraction ionization mass spectrometry method | |
| CN104655775B (en) | The assay method of 3-acetyl group-2,5-thioxene in a kind of edible essence spice | |
| CN105738460A (en) | LC-Q-TOF/MS detection technology for 544 pesticide residues in leaf vegetables | |
| CN201348623Y (en) | Neutral desorption device and neutral desorption electron-spray ionization extraction mass spectrography system | |
| CN106198806A (en) | The assay method of acetaldehyde in a kind of tobacco juice for electronic smoke | |
| CN108760920A (en) | A method of cyazofamid and its metabolite residue amount are measured based on HPLC-MSMS methods | |
| CN105784900A (en) | LC-Q-TOF/MS detection technique for 544 pesticide residues in solanaceous fruit vegetables | |
| CN105158372B (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN105588910B (en) | The methods of risk assessment that plastic products migration thing influences on wine product | |
| CN103412077A (en) | Method for measuring indazole flusulfamide residue amount | |
| CN105445360A (en) | Method for quickly detecting dichlorvos in honey through ND-EESI-MS (neutral desorption-extractive electrospray ionization-mass spectrography) | |
| CN105784898A (en) | LC-Q-TOF/MS detection technique for 544 pesticide residues in citrus fruits | |
| CN105606693B (en) | The method that electron spray extraction ionization mass spectrometry directly detects five kinds of chemical pollutants in propolis | |
| CN104991020A (en) | Liquid chromatography-tandem mass spectrometry test method of wilforlide, triptonide, triptolide and tripterine | |
| CN106546672A (en) | A kind of residue analysis method of polyoxin on ginseng |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211122 Address after: 344300 Industrial Park, Le'an County, Fuzhou City, Jiangxi Province Patentee after: JIANGXI MOUNTAIN BEE FOOD CO.,LTD. Address before: 999 No. 330031 Jiangxi province Nanchang Honggutan University Avenue Patentee before: Nanchang University |
|
| TR01 | Transfer of patent right |