CN115267011B - Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics - Google Patents

Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics Download PDF

Info

Publication number
CN115267011B
CN115267011B CN202211085068.5A CN202211085068A CN115267011B CN 115267011 B CN115267011 B CN 115267011B CN 202211085068 A CN202211085068 A CN 202211085068A CN 115267011 B CN115267011 B CN 115267011B
Authority
CN
China
Prior art keywords
ion
retention time
child
parent
parent ion
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
Application number
CN202211085068.5A
Other languages
Chinese (zh)
Other versions
CN115267011A (en
Inventor
郑抒
谢静
秦剑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing Institute for Food and Drug Control
Original Assignee
Chongqing Institute for Food and Drug Control
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chongqing Institute for Food and Drug Control filed Critical Chongqing Institute for Food and Drug Control
Priority to CN202211085068.5A priority Critical patent/CN115267011B/en
Publication of CN115267011A publication Critical patent/CN115267011A/en
Application granted granted Critical
Publication of CN115267011B publication Critical patent/CN115267011B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Library & Information Science (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention provides a liquid chromatography-mass spectrometry method for detecting 34 drugs of oil-control cosmetics illegally added by adopting a liquid chromatography-mass spectrometry chromatograph, wherein the elution condition of the liquid chromatography is gradient elution. The mass spectrum conditions are as follows: the ion source is an electrospray ion source; the monitoring mode is a positive ion multi-ion reaction monitoring mode; the ion source voltage is 3500V; the sheath gas pressure is 35Arb; the ion transmission tube temperature is: 350 ℃; the atomization temperature was 350 ℃. The invention solves the problem of qualitative detection of various unknown illegal additions in oil-controlled cosmetics in the field of medicine supervision, and solves the problems of screening difficulty and high detection cost of the traditional method; meanwhile, the invention has simple pretreatment, high sensitivity, high flux and accurate qualitative and quantitative analysis.

Description

Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics
Technical Field
The invention relates to a detection method, in particular to a liquid chromatography-mass spectrometry method for qualitatively detecting illegal addition of a drug to an oil-control cosmetic.
Background
The sebaceous glands of human body secrete grease to the skin surface to form a layer of film, and the film is used as one of the components of the skin chemical barrier to play important roles in moisturizing and the like. Excessive secretion of grease can cause full gloss, rough skin and large pores, which can be annoying. The main factors influencing the secretion of sebaceous gland grease are that besides the outside air temperature and the secretion of male hormone of human body, the grease secretion is also influenced by the lipophagic microorganisms such as malassezia, propionibacterium, parasites and the like in the skin. The secretion of grease creates a good living environment for the lipophilic microorganisms, parasites, etc., but their excessive proliferation will cause a series of skin problems.
Aiming at the problem of vigorous grease secretion of the facial skin caused by abnormal propagation of fungi or parasites, the antifungal and antiparasitic drugs are clinically used for killing the fungi and parasites so as to achieve the treatment purpose, and can help to treat acne, comedo, acne and the like caused by further facial oil extraction. Some illegal cosmetic manufacturers illegally add antibacterial and antiparasitic drugs into cosmetics to achieve the effect of oil control or acne removal declared by the products, and even the products can be marked as acarid removal directly on the outer package of the products. In order to keep the skin proper amount of grease, moisten and soft, not to be greasy, the cosmetics produced by a plurality of manufacturers are declared to have the effect of controlling oil so as to attract consumers. However, according to the documents of "pharmaceutical administration" and "safety technical Specification for cosmetics", etc., the pharmaceutical ingredients cannot be added to cosmetics. In the existing cosmetic detection standard of China (cosmetic safety technical Specification), the standard regulation and detection method related to the medicines are mostly antifungal medicines, and the standard regulation and detection method comprises 9 components such as fluconazole, 7 components such as meramamycin hydrochloride, 10 components such as enoxacin, 7 components such as minoxidil, azithromycin in anti-infection medicines and the like; the related antiparasitic drugs are few, including sulfanilamide drugs such as quinine, metronidazole, sulfapyridine and the like. There is still a large number of antiparasitic drugs which are not included in the monitoring area, and which have no corresponding limit requirements and detection methods, and which lack safety supervision, so that it is necessary to risk evaluate the type and content of such drugs which may be present in the "oil-control" cosmetics, and at the same time to establish corresponding inspection and detection techniques for quality management. There are about 34 commonly used antiparasitic drugs that are in the regulatory blank, lacking detection methods, with no limitation in cosmetic safety Specification (2015 edition).
Disclosure of Invention
There are about 34 drugs, according to law enforcement practices by regulatory authorities, that are commonly used antiparasitic drugs that are left blank from regulatory compliance prior to effective administration. The invention provides a detection method which is simple in pretreatment, high in sensitivity, high in flux, and accurate in qualitative and quantitative, is established under the condition of complex matrix interference, and can be used for examining whether the established method can meet the detection requirement of the actual declared oil-control cosmetics, increasing detection objects as much as possible, improving the existing standard, striking illegal addition in the cosmetics and meeting the safety supervision requirement of the cosmetics. The specific invention comprises the following steps: the method comprises the steps of sample preparation and detection by a liquid chromatography, wherein the liquid chromatography is adopted to detect and control the illegal addition of hydroxychloroquine, chloroquine, ethazine, levamisole, dinotefuran, imidacloprid, quinine, pyrimethamine, primaquine, toldazole, chlorantraniliprole, chlorfenphos, mefloquin hydrochloride, albendazole, dichlonit, praziquantel, ethiprole, artemisinin, benmite, cyflumetofen, clofentezine, hexythiazox, spiromesifen, propargite, etoxazole, niclosamide, fenpyroximate, abamectin, pyridaben, doramectin, moxidectin, fenazaquin and ivermectin; the liquid chromatography conditions are as follows: c 18 column, wherein the mobile phase A is ammonium formate-formic acid aqueous solution, the mobile phase B is ammonium formate-formic acid methanol solution, and the column temperature is as follows: 35 ℃, sample injection amount: 2 μl, flow rate: 0.3mL/min; the gradient elution conditions were:
0-2min,50-50% mobile phase B;
2-5min,50-90% mobile phase B;
5-9min,90-90% mobile phase B;
9-10min,90-50% mobile phase B;
10-12min,50-50% mobile phase B.
The mass spectrum conditions are as follows: the ion source is an electrospray ion source; the monitoring mode is a positive ion multi-ion reaction monitoring mode; the ion source voltage is 3500V; the sheath gas pressure is 35Arb; the ion transmission tube temperature is: 350 ℃; the atomization temperature was 350 ℃.
The monitoring ion pairs of 34 components and relevant voltage parameters are set as follows: the retention time of hydroxychloroquine is 0.90min, the parent ion 336.28m/z, the RF Lens 157V, the child ion 179.083m/z, 247.083 * m/z, CE36V and 20V; the retention time of chloroquine is 0.92min, the parent ion 320.28m/z, the RF Lens 144V, the child ion 142.167m/z, 247.083 * m/z, the CE 21.18V and the CE 18.45V; the retention time of the ethazine is 0.92min, the parent ion 200.28m/z, the RF Lens 97V, the child ion 100.167 * m/z, 127.167m/z, CE14.55V and 13.9V; levamisole has a retention time of 0.96min, parent ion 205.17m/z, RF Lens 135V, daughter ion 123.083m/z, 177.97 * m/z, CE27.7V, 20.92V; the retention time of dinotefuran is 0.96min, parent ion 203.21m/z, RF Lens 73V, child ion 113.167 x m/z, 129.167m/z, CE 10.23V, 10.23V; the retention time of imidacloprid is 1.21min, the parent ion 256.16m/z, RF Lens98V, the child ion 175.083m/z, 209.083 * m/z, CE 17.51V and 15.31V; quinine retention time 1.52min, parent ion 325.29m/z, RF Lens 184V, daughter ion 172.083 * m/z, 198.083m/z, CE 33.43V, 24.94V; the retention time of pyrimethamine is 1.69min, the parent ion 249.17m/z, the RF Lens 166V, the child ion 177m/z, 233.012 * m/z, CE28.77V and 28.46V; the retention time of primaquine is 2.46min, the parent ion 260.22m/z, RF Lens 96V, the child ion 175.083m/z, 243.095 * m/z, CE12.39V and 10.23V; the retention time of the mebendazole is 4.43min, the parent ion 296.21m/z, the RF Lens 173V, the child ion 105.167m/z, 264.083 * m/z and the CE
32.75V, 20.39V; the retention time of chlorantraniliprole is 4.92min, parent ion 484.1m/z, RF Lens176
V, ion 285.917m/z, 452.946 * m/z, CE 10.23V, 19.06V; the retention time of the fenphos is 4.94min, the parent ion 241.15m/z, the RF Lens 90V, the child ion 125m/z, 209 * m/z, CE 18.64V and 10.23V; mefloquine hydrochloride retention time is 5.28min, parent ion 379.24m/z, RF Lens 189V, child ion 321.083m/z, 361.095 * m/z, CE 29.33V, 22.4V; the retention time of albendazole is 5.44min, the parent ion 266.16m/z, the RF Lens 176V, the child ion 191m/z, 234 * m/z, CE 31.72V and 19.02V; the retention time of the dichloropnit is 5.44min, the parent ion 234.12m/z, the RF Lens 213V, the child ion 159.083m/z, 191 * m/z, the CE 26.64V and the CE 23.16V; the retention time of praziquantel is 5.44min, the parent ion 313.26m/z, RF Lens 154V, the child ion 174.083m/z, 203.083 * m/z, CE 26.6V and 15.31V; the retention time of ethiprole is 5.46min, the parent ion 397.15m/z, RF Lens190V, the child ion 255m/z, 351 * m/z, CE 34.41V and 19.36V; the retention time of artemisinin is 5.67min, the parent ion 283.27m/z, the RF Lens 62V, the child ion 151.095m/z, 247.095 * m/z, the CE 14.32V and the CE 10.23V; the retention time of the fenpyroximate is 6.56min, the parent ion 364.241m/z, the RF Lens 88V, the child ion 105.155m/z, the child ion 199 * m/z, the CE 23.16V and the CE 10.23V; the retention time of the cyflumetofen is 6.78min, the parent ion 465.38m/z, the RF Lens 150V, the child ion 173.042 * m/z, 249.125m/z, the CE 24.71V and the CE 12.65V; the retention time of clofentezine is 6.79min, parent ion 303.2m/z, RF Lens 111V, daughter ion 102.2m/z, 138.1 * m/z, CE 32.48V, 14.17V; the retention time of the hexythiazox is 7.21min, the parent ion 353.36m/z, the RF Lens 141V, the child ion 168.071m/z, 228 * m/z, CE23.08V and 14.59V; the retention time of spiromesifen is 7.23min, the parent ion 388.486m/z, RF Lens86V, the child ion 255.137m/z, 273.167 x m/z, CE26.3V and 10.23V; retention time of propargite is 7.28min, parent ion is 368.3m/z, RF Lens is 108V, child ion is 175.083m/z, 231.167 * m/z, CE14.97V and 10.23V; the retention time of etoxazole is 7.36min, the parent ion 360.3m/z, the RF Lens 170V, the child ion 141.083 * m/z, 304.167m/z, the CE 29.3V and the CE 17.33V; the retention time of niclosamide is 7.40min, the parent ion 327.04m/z, the RF Lens 175V, the child ion 172.929m/z, 290.988 * m/z, CE 26.91V and 17.05V; the retention time of spirodiclofen is 7.44min, the parent ion 411.29m/z, RF Lens 115V, the child ion 71.363m/z, 313.101 * m/z, CE 14.21V, 10.23V; the retention time of fenpyroximate is 7.61min, the parent ion 422.37m/z, RF Lens 165V, the child ion 214.113m/z, 366.167 * m/z, CE 28.35V and 14.97V; the retention time of abamectin is 7.76min, the parent ion 895.74m/z, the RF Lens 299V, the child ion 607.429m/z, 751.625 * m/z, the CE 41.12V and the CE 37.11V; the retention time of pyridaben is 7.82min, the parent ion is 365.25m/z, the RF Lens is 126V, the child ion is 147.125m/z, 309.042 * m/z, CE23.46V and 10.99V; doramectin retention time 8.18min, parent ion 916.79m/z, RF Lens 206V, daughter ion 333.286m/z, 593.476 * m/z, CE 16.37V, 10.23V; moxidectin retention time 8.38min, parent ion 640.68m/z, RF Lens 163V, daughter ion 498.429m/z, 528.429 * m/z, CE 12.2V, 10.23V; the retention time of fenazaquin is 8.37min, the parent ion 307.28m/z, the RF Lens 139V, the child ion 147.083m/z, 161.095 * m/z, the CE 18.42V and the CE 16.22V; the retention time of ivermectin is 8.72min, the parent ion 892.8m/z, the RF Lens 189V, the child ion 307.25m/z, 569.5m/z, the CE 20.96V and 12.01V; the ionization mode of the niclosamide in the 34 components is ESI -, and the ionization mode of the other components is ESI +,*, which is a quantitative ion pair.
The preparation method of the liquid water-based and oil-like sample in the sample preparation comprises the following steps: liquid water-based and oily: weighing the sample, placing the sample into a centrifuge tube with a plug, adding methanol, carrying out vortex oscillation for 30s, fully and uniformly mixing the sample and an extraction solvent, carrying out ultrasonic extraction for 20min, standing to room temperature, fixing the volume with the methanol, shaking uniformly, and centrifuging for 10min at 10000r/min if necessary; filtering the supernatant with a 0.22 μm filter membrane, and taking the filtrate as a sample solution to obtain liquid water-based and oily samples.
The preparation method of the cream emulsion type sample in the sample preparation comprises the following steps: weighing the sample, placing the sample into a centrifuge tube with a plug, adding saturated aqueous solution of sodium chloride, stirring for 30s to disperse the sample, adding methanol, stirring for 30s, fully mixing the sample with the extraction solvent, performing ultrasonic extraction for 20min, standing to room temperature, fixing the volume to 10mL with methanol, shaking, and centrifuging for 10min at 10000r/min if necessary. Filtering the supernatant with a 0.22 μm filter membrane, and taking the filtrate as a sample solution to obtain a cream emulsion sample.
The beneficial technical effects of the invention are as follows: the invention solves the problem of qualitative detection of various unknown illegal additions in oil-controlled cosmetics in the field of medicine supervision, and solves the problems of screening difficulty and high detection cost of the traditional method; meanwhile, the invention has simple pretreatment, high sensitivity, high flux and accurate qualitative and quantitative analysis.
Drawings
FIG. 1 is a total ion flow diagram of 34 components;
FIG. 2 is a multi-reaction monitoring chromatogram of a standard solution of niclosamide (RT: 7.40 min);
FIG. 3 Multi-reaction monitoring chromatogram of a standard solution of ethazine (RT: 0.92 min);
FIG. 4 is a multi-reaction monitoring chromatogram of dinotefuran (RT: 0.96 min) standard solution;
FIG. 5 is a multi-reaction monitoring chromatogram of levamisole (RT: 0.96 min) standard solution;
FIG. 6 multiple reaction monitoring chromatogram of standard solution of dichloroniter (RT: 5.44 min);
FIG. 7 is a multi-reaction monitoring chromatogram of a standard solution of chlorfenpyr (RT: 4.94 min);
FIG. 8 Multi-reaction monitoring chromatogram of pyrimethamine (RT: 1.69 min) standard solution;
FIG. 9 is a multi-reaction monitoring chromatogram of an imidacloprid (RT: 1.21 min) standard solution;
FIG. 10 is a multi-reaction monitoring chromatogram of a primary aminoquin (RT: 2.46 min) standard solution;
FIG. 11 multiple reaction monitoring chromatogram of albendazole (RT: 5.44 min) standard solution;
FIG. 12 Multi-reaction monitoring chromatogram of artemisinin (RT: 5.67 min) standard solution;
FIG. 13 multiple reaction monitoring chromatogram of a standard solution of toldazole (RT: 4.43 min);
FIG. 14 Multi-reaction monitoring chromatogram of a clofentezine (RT: 6.79 min) standard solution;
FIG. 15 is a multi-reaction monitoring chromatogram of a standard solution of fenazaquin (RT: 8.37 min);
FIG. 16 is a multi-reaction monitoring chromatogram of a standard solution of praziquantel (RT: 5.44 min);
FIG. 17 multiple reaction monitoring chromatogram of chloroquine (RT: 0.92 min) standard solution;
FIG. 18 Multi-reaction monitoring chromatogram of quinine (RT: 1.52 min) standard solution;
FIG. 19 is a multi-reaction monitoring chromatogram of a hydroxychloroquine (RT: 0.90 min) standard solution;
FIG. 20 Multi-reaction monitoring chromatogram of a standard solution of hexythiazox (RT: 7.21 min);
FIG. 21 Multi-reaction monitoring chromatogram of etoxazole (RT: 7.36 min) standard solution;
FIG. 22 multiple reaction monitoring chromatogram of a benomyl (RT: 6.56 min) standard solution;
FIG. 23 is a multi-reaction monitoring chromatogram of a standard solution of pyridaben (RT: 7.82 min);
FIG. 24 is a multi-reaction monitoring chromatogram of propargite (RT: 7.28 min) standard solution;
FIG. 25 is a multi-reaction monitoring chromatogram of a standard solution of mefloquine hydrochloride (RT: 5.28 min);
FIG. 26 multiple reaction monitoring chromatogram of spiromesifen (RT: 7.23 min) standard solution;
FIG. 27 is a multi-reaction monitoring chromatogram of ethiprole (RT: 5.46 min) standard solution;
FIG. 28 multiple reaction monitoring chromatogram of spirodiclofen (RT: 7.44 min) standard solution;
FIG. 29 multiple reaction monitoring chromatogram of fenpyroximate (RT: 7.61 min) standard solution;
FIG. 30 is a multi-reaction monitoring chromatogram of a standard solution of cyflumetofen (RT: 6.78 min);
FIG. 31 multiple reaction monitoring chromatogram of chlorantraniliprole (RT: 4.92 min) standard solution;
FIG. 32 Multi-reaction monitoring chromatogram of moxidectin (RT: 8.38 min) standard solution;
FIG. 33 Multi-reaction monitoring chromatogram of ivermectin (RT: 8.72 min) standard solution;
FIG. 34 Multi-reaction monitoring chromatogram of Avermectin (RT: 7.76 min) standard solution;
FIG. 35 Multi-reaction monitoring chromatogram of doramectin (RT: 8.18 min) standard solution.
Detailed Description
EXAMPLE 1 establishment of chromatographic methods
1 Experimental facility: liquid chromatography-mass spectrometry: thermo Vanquish/TSQ Endura LC/MS/MS; mass spectrometry software: TRACE FINDER.
2 Chromatographic conditions
Chromatographic column: thermo Hypersil GOLD aQC18 column (100 mm. Times.2.1 mm. Times.1.9 μm)
Mobile phase: a: ammonium formate-aqueous formic acid (0.1261 g of ammonium formate was weighed, dissolved and diluted to 1000mL with 0.01% aqueous formic acid, filtered through a 0.22 μm filter);
B: ammonium formate-methanoic acid solution (0.1261 g of ammonium formate, dissolved in 0.01% methanoic acid solution and diluted to 1000mL, filtered through a 0.22 μm filter) gradient procedure is given in table 1:
TABLE 1 gradient elution procedure
Flow rate: 0.3mL/min;
Column temperature: 35 ℃;
Sample injection amount: 2. Mu.L;
3 Mass Spectrometry Condition
Ion source: electrospray ion source (ESI source);
Monitoring mode: a positive ion polyion reaction monitoring mode; monitoring ion pairs and related voltage parameter settings are shown in table 2;
ion source voltage: 3,500V;
Sheath air pressure (Arb): 35;
Ion transport tube temperature (c): 350;
atomization temperature (deg.c): 350.
TABLE 2 ion pair for 34 components and related voltage parameter setting table
* : Ion pairs were quantified.
4 Sources of reference:
Table 334 relevant information of component reference
Example 2 preparation of experimental samples
Method study samples: all commercial samples were: yeast amino acid facial cleanser (emulsion cream type), chlorella skin lotion (liquid water-based type), kernel and artisan old vinegar Wang Muyu lotion (oily type).
1 Control solution
Preparing a reference substance solution: precisely weighing each reference substance, respectively placing into 10mL volumetric flasks, dissolving with methanol, and fixing volume to obtain reference substance stock solution with concentration of 1mg/mL, and storing the stock solution in a refrigerator at 0-4deg.C. Respectively precisely measuring a proper amount of reference substance stock solution, adding methanol for dilution to a scale, shaking uniformly to obtain a mixed standard solution, precisely measuring mixed standard solutions with different volumes, and adding methanol for dilution to a constant volume to obtain a standard series of solutions.
2 Preparation of sample solution
Liquid water-based and oily: weighing 0.2g (accurate to 0.0001 g) of the sample, placing the sample into a 15mL centrifuge tube with a plug, adding about 8mL of methanol, carrying out vortex oscillation for 30s, fully mixing the sample with an extraction solvent, carrying out ultrasonic extraction for 20min, standing to room temperature, fixing the volume to 10mL with methanol, shaking, and centrifuging for 10min at 10000r/min if necessary. The supernatant was filtered through a 0.22 μm filter membrane, and the filtrate was used as a sample solution.
Cream emulsions: 0.2g (accurate to 0.001 g) of the sample is weighed, placed in a 15mL centrifuge tube with a plug, 1.0mL of saturated aqueous solution of sodium chloride is added, vortex oscillation is carried out for 30s to disperse the sample, about 7mL of methanol is added, vortex oscillation is carried out for 30s to fully mix the sample with the extraction solvent, ultrasonic extraction is carried out for 20min, the mixture is stood to room temperature, methanol is used for constant volume to 10mL, shaking is carried out, and centrifugation is carried out for 10min at 10000r/min if necessary. The supernatant was filtered through a 0.22 μm filter membrane, and the filtrate was used as a sample solution.
5.3 Preparation of the labeling solution
Adding a marking solution: 0.2g of blank samples (6 parts of each of 3 matrixes of liquid water-based samples, emulsion creams and oily samples) are weighed for 18 parts, placed in a centrifuge tube with a plug, and mixed standard solutions with different levels of low, medium and high are respectively added, wherein each level is 6 parts in parallel. And (5) treating according to a preparation method of the sample solution to obtain the labeled recovery liquid.
The standard adding levels of the low, medium and high concentrations are respectively the quantitative limit concentration (linear lowest point), 25 times of the quantitative limit concentration and 50 times of the quantitative limit concentration (linear highest point) of each component.
EXAMPLE 3 Linear Studies
The linearity of 34 components was examined according to the chromatographic and mass spectrometric conditions of example 1, and the results show that the linear correlation coefficient r is good and is above 0.996. The specific data are shown in Table 4.
1 Detection limit and quantitative limit
The quantitative limit was obtained by diluting the corresponding standard solution to the 10-fold signal-to-noise ratio of the instrument (S/n=10) respectively, and taking this point as the linear nadir. The detection concentration and the quantitative concentration were calculated with a sample weighing amount of 0.2g and a constant volume of 10 mL. The specific data are shown in Table 4.
TABLE 4 Linear Range, linear equation, correlation coefficient, detection Limit and quantitative Limit for 34 component standards
EXAMPLE 4 precision study
Precision within 1 day
The Relative Standard Deviation (RSD) of the peak areas was measured at 0,4,8, 12, 16, 20, 24h for the low concentration solution (linear minimum) and the high concentration solution (linear maximum), respectively, and the measurement results are shown in table 5.
TABLE 5 within-day precision of 34 Components
Sequence number Component name Low concentration RSD (%) High concentration RSD (%)
1 Hydroxychloroquine 3.22 7.42
2 Chloroquine 2.93 6.52
3 Ethanamine oxazine 4.27 4.10
4 Levamisole 5.42 5.84
5 Dinotefuran 5.49 2.21
6 Imidacloprid 3.33 2.05
7 Quinine (quinine) 6.00 6.64
8 Pyrimethamine 6.87 5.57
9 Primaquine 4.90 3.61
10 Toluene dazole 2.73 2.19
11 Chlorantraniliprole 6.59 3.71
12 Acarid aversion 6.52 3.48
13 Mefloquine hydrochloride 6.59 6.19
14 Albendazole 3.57 1.51
15 Dichloro nit 6.45 5.35
16 Praziquantel 2.91 1.79
17 Ethiprole 6.94 1.61
18 Artemisinin 4.16 5.08
19 Benmite-killing agent 3.55 1.42
20 Cyflumetofen 5.30 1.14
21 Clofentezine 6.48 3.02
22 Thifen-methyl 7.25 6.67
23 Spiromesifen 4.39 4.63
24 Propargite medicine 5.01 6.01
25 Etoxazole 1.97 3.52
26 Niclosamide 5.10 3.92
27 Spirodiclofen 6.76 3.78
28 Fenpyroximate 3.35 2.05
29 Avermectins 2.23 6.25
30 Pyridaben medicine 6.58 4.54
31 Doramectin 2.38 4.14
32 Moxidectin 3.75 5.91
33 Fenazaquin 4.65 3.29
34 Ivermectin 6.91 7.47
Precision of 2 days
The Relative Standard Deviation (RSD) of the peak area measured in 3 days was examined for a low concentration solution (linear lowest point) and a high concentration solution (linear highest point), respectively, and the measurement results are shown in table 6.
TABLE 6 daytime precision of 34 Components
Sequence number Component name Low concentration RSD (%) High concentration RSD (%)
1 Hydroxychloroquine 6.74 3.44
2 Chloroquine 5.84 6.83
3 Ethanamine oxazine 5.87 0.90
4 Levamisole 3.83 3.27
5 Dinotefuran 2.74 4.62
6 Imidacloprid 2.23 7.21
7 Quinine (quinine) 7.26 5.67
8 Pyrimethamine 3.46 4.64
9 Primaquine 4.83 6.24
10 Toluene dazole 6.24 7.07
11 Chlorantraniliprole 2.80 7.54
12 Acarid aversion 2.56 4.00
13 Mefloquine hydrochloride 3.99 6.25
14 Albendazole 0.43 2.82
15 Dichloro nit 2.47 6.83
16 Praziquantel 2.98 1.92
17 Ethiprole 6.14 4.62
18 Artemisinin 3.40 2.32
19 Benmite-killing agent 6.70 2.28
20 Cyflumetofen 2.94 23.87
21 Clofentezine 0.94 4.12
22 Thifen-methyl 5.66 3.89
23 Spiromesifen 3.96 4.06
24 Propargite medicine 5.96 5.01
25 Etoxazole 5.73 2.12
26 Niclosamide 2.19 7.03
27 Spirodiclofen 5.39 2.34
28 Fenpyroximate 6.65 0.40
29 Avermectins 5.70 7.24
30 Pyridaben medicine 3.24 7.39
31 Doramectin 2.60 0.71
32 Moxidectin 3.91 7.14
33 Fenazaquin 2.48 1.69
34 Ivermectin 3.70 7.14
EXAMPLE 5 recovery study
The standard recovery rates of the low, medium and high concentrations were examined according to the aforementioned chromatographic, mass spectrometric conditions and treatment methods for the standard solution, and the average recovery rate and the Relative Standard Deviation (RSD) were calculated, and the results are shown in table 7.
The standard adding levels of the low, medium and high concentrations are respectively the quantitative limit concentration (standard curve lowest point), 25 times of the quantitative limit concentration and 50 times of the quantitative limit concentration (standard curve highest point) of each component.
Table 7 labeled recovery and precision of 34 components (n=6)
EXAMPLE 6 stability
Stability within 1 day
The peak areas of the low concentration solution (linear lowest point) and the high concentration solution (linear highest point) are measured at 0,4,8, 12, 16, 20 and 24 hours respectively, the peak areas are substituted into a standard curve to calculate the concentration of the measured substance, and the accuracy and the Relative Standard Deviation (RSD) of the measured substance are calculated, and the measurement results are shown in Table 8;
TABLE 8 within-day precision of 34 Components
2 Day stability
The measured peak areas of the low concentration solution (linear lowest point) and the high concentration solution (linear highest point) within 3 days were examined, the concentrations of the measured substances were calculated by substituting the standard curve, and the accuracy and Relative Standard Deviation (RSD) thereof were calculated, and the measurement results are shown in table 9.
TABLE 9 daytime stability of 34 Components

Claims (2)

1. The liquid chromatography-mass spectrometry method for qualitatively detecting illegally added medicines of oil-control cosmetics comprises sample preparation and detection by a liquid chromatography-mass spectrometry, and is characterized in that: synchronously detecting and controlling the illegal addition of hydroxychloroquine, chloroquine, ethazine, levamisole, dinotefuran, imidacloprid, quinine, pyrimethamine, primaquine, fenbendazole, chlorantraniliprole, fenbuconazole, mefloquine hydrochloride, albendazole, praziquantel, ethiprole, artemisinin, benomyl, cyflumetofen, clofentezine, hexythiazox, spiromesifen, propargite, etoxazole, niclosamide, spirodiclofen, fenpyrad, abamectin, pyridaben, doramectin, moxidectin, fenazaquin and ivermectin by adopting a liquid chromatography; the liquid chromatography conditions are as follows: c 18 column, wherein the mobile phase A is ammonium formate-formic acid aqueous solution, the mobile phase B is ammonium formate-formic acid methanol solution, and the column temperature is as follows: 35 ℃, sample injection amount: 2. mu L, flow rate: 0.3 mL/min; the gradient elution conditions were:
0-2min,50-50% mobile phase B;
2-5min,50-90% mobile phase B;
5-9min,90-90% mobile phase B;
9-10min,90-50% mobile phase B;
10-12min,50-50% mobile phase B;
the mass spectrum conditions are as follows: the ion source is an electrospray ion source; the monitoring mode is a positive ion multi-ion reaction monitoring mode; the ion source voltage is 3500V; the sheath gas pressure is 35 Arb; the ion transmission tube temperature is: 350 ℃; the atomization temperature is 350 ℃;
The preparation method of the liquid water-based and oil-like sample in the sample preparation comprises the following steps: liquid water-based and oily: weighing the sample, placing in a centrifuge tube with a plug, adding methanol, shaking by vortex for 30s to fully mix the sample with the extraction solvent, extracting by ultrasound for 20min, standing to room temperature, fixing the volume with methanol, shaking, and centrifuging at 10000 r/min for 10min; filtering the supernatant with a 0.22 μm filter membrane, and taking the filtrate as a sample solution to obtain liquid water-based and oily samples;
The preparation method of the cream emulsion type sample in the sample preparation comprises the following steps: weighing a sample, placing the sample into a centrifuge tube with a plug, adding saturated aqueous solution of sodium chloride, carrying out vortex oscillation for 30s to disperse the sample, adding methanol, carrying out vortex oscillation for 30s to fully mix the sample with an extraction solvent, carrying out ultrasonic extraction for 20min, standing to room temperature, fixing the volume to 10mL with methanol, shaking uniformly, centrifuging for 10min at 10000 r/min, filtering the supernatant with a 0.22 mu m filter membrane, and taking the filtrate as a sample solution to obtain a cream emulsion sample.
2. The liquid chromatography-mass spectrometry method for the qualitative detection of illegal addition of drugs to oil-control cosmetics according to claim 1, characterized in that: the monitored ion pairs and associated voltage parameters for the 34 components were set as: the retention time of hydroxychloroquine is 0.90 min, the parent ion 336.28 m/z, RF Lens157V, the child ion 179.083m/z, 247.083 * m/z, CE36V, 20V; the retention time of chloroquine is 0.92 min, the parent ion 320.28 m/z, the RF Lens144V, the child ion 142.167m/z, 247.083 * m/z, CE 21.18V and 18.45V; the retention time of the ethazine is 0.92 min, the parent ion 200.28 m/z, the RF Lens97V, the child ion 100.167 * m/z, 127.167m/z, CE14.55V and 13.9V; levamisole retention time is 0.96 min, parent ion 205.17 m/z, RF Lens135V, child ion 123.083m/z, 177.97 * m/z, CE27.7V, 20.92V; dinotefuran retention time 0.96 min, parent ion 203.21 m/z, RF Lens73V, daughter ion 113.167 x m/z, 129.167m/z, CE10.23V, 10.23V; the retention time of imidacloprid is 1.21 min, the parent ion 256.16 m/z, RF Lens98V, the child ion 175.083m/z, 209.083 * m/z, CE17.51V, 15.31V; quinine retention times 1.52 min, parent ion 325.29 m/z, RF Lens184V, daughter ion 172.083 * m/z, 198.083m/z, CE33.43V, 24.94V; the retention time of pyrimethamine is 1.69 min, the parent ion 249.17 m/z, the RF Lens166V, the child ion 177m/z, 233.012 * m/z, CE28.77V and 28.46V; the retention time of primaquine is 2.46 min, parent ion 260.22 m/z, RF Lens96V, child ion 175.083m/z, 243.095 * m/z, CE12.39V, 10.23V; the retention time of the mebendazole is 4.43 min, the parent ion 296.21 m/z, the RF Lens173V, the child ion 105.167m/z, 264.083 * m/z, the CE 32.75V and the CE 20.39V; the retention time of chlorantraniliprole is 4.92 min, parent ion 484.1 m/z, RF Lens176V, child ion 285.917m/z, 452.946 * m/z, CE10.23V, 19.06V; the retention time of the fenphos is 4.94 min, the parent ion 241.15 m/z, the RF Lens90V, the child ion 125m/z, 209 * m/z, CE 18.64V and 10.23V; mefloquine hydrochloride retention time 5.28 min, parent ion 379.24 m/z, RF Lens189V, child ion 321.083m/z, 361.095 * m/z, CE 29.33V, 22.4V; the retention time of albendazole is 5.44 min, the parent ion 266.16 m/z, the RF Lens176V, the child ion 191m/z, 234 * m/z, CE 31.72V and 19.02V; the retention time of the dichloropnit is 5.44 min, the parent ion 234.12 m/z, the RF Lens213V, the child ion 159.083m/z, 191 * m/z, CE 26.64V and 23.16V; praziquantel has a retention time of 5.44 min, parent ion 313.26 m/z, RF Lens154V, child ion 174.083m/z, 203.083 * m/z, CE 26.6V, 15.31V; the retention time of ethiprole is 5.46 min, the parent ion 397.15 m/z, RF Lens190V, the child ion 255m/z, 351 * m/z, CE 34.41V and 19.36V; the retention time of artemisinin is 5.67 min, the parent ion 283.27 m/z, RF Lens62V, the child ion 151.095m/z, 247.095 * m/z, CE 14.32V, 10.23V; the retention time of the fenpyroximate is 6.56 min, the parent ion 364.241 m/z, the RF Lens88V, the child ion 105.155m/z, 199 * m/z, CE 23.16V and 10.23V; the retention time of the cyflumetofen is 6.78 min, the parent ion 465.38 m/z, the RF Lens150V, the child ion 173.042 * m/z, 249.125m/z, the CE 24.71V and the CE 12.65V; the retention time of clofentezine is 6.79 min, parent ion 303.2 m/z, RF Lens111V, child ion 102.2m/z, 138.1 * m/z, CE 32.48V, 14.17V; retention time of hexythiazox 7.21 min, parent ion 353.36 m/z, RF Lens141V, child ion 168.071m/z, 228 * m/z, CE23.08V, 14.59V; the retention time of spiromesifen is 7.23 min, parent ion 388.486 m/z, RF Lens 86V, child ion 255.137m/z, 273.167 * m/z, CE26.3V, 10.23V; retention time of propargite is 7.28 min, parent ion is 368.3 m/z, RF Lens is 108V, child ion is 175.083m/z, 231.167 * m/z, CE14.97V and 10.23V; the retention time of etoxazole is 7.36 min, the parent ion 360.3 m/z, the RF Lens170V, the child ion 141.083 * m/z, 304.167m/z, CE 29.3V and 17.33V; niclosamide retention time 7.40 min, parent ion 327.04 m/z, RF Lens175V, child ion 172.929m/z, 290.988 * m/z, CE 26.91V, 17.05V; the retention time of spirodiclofen is 7.44 min, parent ion 411.29 m/z, RF Lens115V, child ion 71.363m/z, 313.101 * m/z, CE14.21V, 10.23V; the retention time of fenpyroximate is 7.61 min, the parent ion 422.37 m/z, RF Lens165V, the child ion 214.113m/z, 366.167 * m/z, CE28.35V and 14.97V; the retention time of abamectin is 7.76 min, the parent ion 895.74 m/z, the RF Lens299V, the child ion 607.429m/z, 751.625 * m/z, CE 41.12V and 37.11V; the retention time of pyridaben is 7.82 min, parent ion 365.25 m/z, RF Lens126V, child ion 147.125m/z, 309.042 * m/z, CE23.46V, 10.99V; doramectin retention time 8.18 min, parent ion 916.79 m/z, RF Lens206V, daughter ion 333.286m/z, 593.476 * m/z, CE 16.37V, 10.23V; moxidectin has a retention time of 8.38 min, parent ion 640.68 m/z, RF Lens163V, daughter ion 498.429m/z, 528.429 * m/z, CE 12.2V, 10.23V; fenazaquin retention time is 8.37 min, parent ion 307.28 m/z, RF Lens139V, child ion 147.083m/z, 161.095 * m/z, CE 18.42V, 16.22V; the retention time of ivermectin is 8.72min, the parent ion 892.8 m/z, the RF Lens189V, the child ion 307.25m/z, 569.5m/z, and the CE 20.96V and 12.01V; the ionization mode of the niclosamide in the 34 components is ESI -, and the ionization mode of the other components is ESI +,*, which is a quantitative ion pair.
CN202211085068.5A 2022-09-06 2022-09-06 Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics Active CN115267011B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211085068.5A CN115267011B (en) 2022-09-06 2022-09-06 Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211085068.5A CN115267011B (en) 2022-09-06 2022-09-06 Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics

Publications (2)

Publication Number Publication Date
CN115267011A CN115267011A (en) 2022-11-01
CN115267011B true CN115267011B (en) 2024-05-07

Family

ID=83756409

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211085068.5A Active CN115267011B (en) 2022-09-06 2022-09-06 Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics

Country Status (1)

Country Link
CN (1) CN115267011B (en)

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311010A (en) * 2001-04-11 2002-10-23 Teikoku Hormone Mfg Co Ltd Method for determining dihydroavermectine
CN101169400A (en) * 2006-10-24 2008-04-30 广东省保化检测中心有限公司 High efficiency liquid chromatography detection method for sulpha drugs in cosmetic product
CN101498671A (en) * 2009-03-12 2009-08-05 广东省药品检验所 Fast screening method for metronidazole in cosmetic
CN103048401A (en) * 2012-12-07 2013-04-17 中国检验检疫科学研究院 Determining method for 15 kinds of forbidden nitro imidazoles antibiotics in cosmetics
CN103760261A (en) * 2014-01-07 2014-04-30 深圳市谱尼测试科技有限公司 Method for measuring ethanolamine substance residual quantity in cosmetics
CN103776936A (en) * 2014-02-26 2014-05-07 江苏斯威森生物医药工程研究中心有限公司 Method for determining content of ivermectin, albendazole sulfoxide and praziquantel in tetramizole
CN103940922A (en) * 2014-04-08 2014-07-23 中国检验检疫科学研究院 Method for determining five forbidden miticides in cosmetics
CN104198625A (en) * 2014-08-16 2014-12-10 中山鼎晟生物科技有限公司 Rapid detection method of tetracycline antibiotics in cosmetics
CN108051534A (en) * 2017-11-20 2018-05-18 中山大学 A kind of method of the 132 kinds of chemicalses illegally added in rapid screening Chinese patent drug and health products
CN108169381A (en) * 2018-01-26 2018-06-15 昆明理工大学 The detection method of drug is illegally added in a kind of reducing blood lipid class Chinese patent drug and health food
CN111208249A (en) * 2020-01-14 2020-05-29 信阳农林学院 Method for determining content of effective components of anthelmintic by high performance liquid chromatography
CN111474250A (en) * 2020-03-12 2020-07-31 青海省药品检验检测院 Method for simultaneously determining 40 antibiotics in cosmetics
CN112379022A (en) * 2020-11-16 2021-02-19 张宪臣 Detection method for rapidly screening various pesticides and biotoxins in aquatic product
CN112730693A (en) * 2021-01-28 2021-04-30 中国农业科学院饲料研究所 Method for determining pesticide residue in feed by liquid phase-tandem mass spectrometry technology
CN114577950A (en) * 2022-03-15 2022-06-03 浙江省食品药品检验研究院 Method for determining anti-infective drugs in cosmetics
CN114594183A (en) * 2022-03-09 2022-06-07 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） Detection method of 15 forbidden azoles in children cosmetics
CN114935616A (en) * 2022-06-02 2022-08-23 汕头海关技术中心 Method for detecting cosmetic forbidden substances
CN114942289A (en) * 2022-06-02 2022-08-26 贵州大学 Method for determining anticoccidial drugs in water in surrounding environment of farm by liquid chromatography-mass spectrometry

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10914713B2 (en) * 2018-01-23 2021-02-09 Perkinelmer Health Sciences, Inc. Systems and methods for pesticide detection using mass spectroscopy

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311010A (en) * 2001-04-11 2002-10-23 Teikoku Hormone Mfg Co Ltd Method for determining dihydroavermectine
CN101169400A (en) * 2006-10-24 2008-04-30 广东省保化检测中心有限公司 High efficiency liquid chromatography detection method for sulpha drugs in cosmetic product
CN101498671A (en) * 2009-03-12 2009-08-05 广东省药品检验所 Fast screening method for metronidazole in cosmetic
CN103048401A (en) * 2012-12-07 2013-04-17 中国检验检疫科学研究院 Determining method for 15 kinds of forbidden nitro imidazoles antibiotics in cosmetics
CN103760261A (en) * 2014-01-07 2014-04-30 深圳市谱尼测试科技有限公司 Method for measuring ethanolamine substance residual quantity in cosmetics
CN103776936A (en) * 2014-02-26 2014-05-07 江苏斯威森生物医药工程研究中心有限公司 Method for determining content of ivermectin, albendazole sulfoxide and praziquantel in tetramizole
CN103940922A (en) * 2014-04-08 2014-07-23 中国检验检疫科学研究院 Method for determining five forbidden miticides in cosmetics
CN104198625A (en) * 2014-08-16 2014-12-10 中山鼎晟生物科技有限公司 Rapid detection method of tetracycline antibiotics in cosmetics
CN108051534A (en) * 2017-11-20 2018-05-18 中山大学 A kind of method of the 132 kinds of chemicalses illegally added in rapid screening Chinese patent drug and health products
CN108169381A (en) * 2018-01-26 2018-06-15 昆明理工大学 The detection method of drug is illegally added in a kind of reducing blood lipid class Chinese patent drug and health food
CN111208249A (en) * 2020-01-14 2020-05-29 信阳农林学院 Method for determining content of effective components of anthelmintic by high performance liquid chromatography
CN111474250A (en) * 2020-03-12 2020-07-31 青海省药品检验检测院 Method for simultaneously determining 40 antibiotics in cosmetics
CN112379022A (en) * 2020-11-16 2021-02-19 张宪臣 Detection method for rapidly screening various pesticides and biotoxins in aquatic product
CN112730693A (en) * 2021-01-28 2021-04-30 中国农业科学院饲料研究所 Method for determining pesticide residue in feed by liquid phase-tandem mass spectrometry technology
CN114594183A (en) * 2022-03-09 2022-06-07 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） Detection method of 15 forbidden azoles in children cosmetics
CN114577950A (en) * 2022-03-15 2022-06-03 浙江省食品药品检验研究院 Method for determining anti-infective drugs in cosmetics
CN114935616A (en) * 2022-06-02 2022-08-23 汕头海关技术中心 Method for detecting cosmetic forbidden substances
CN114942289A (en) * 2022-06-02 2022-08-26 贵州大学 Method for determining anticoccidial drugs in water in surrounding environment of farm by liquid chromatography-mass spectrometry

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
Analytical methods to analyze pesticides and herbicides;Yifan Wang等;Annual Literature Review;20190624;全文 *
HPLC-PDA检测祛痘除螨类化妆品中非法添加盐酸米诺环素方法的建立;窦佳;董莉;栾爽;沈丹丹;李晓娜;;职业与健康;20150401(第07期);全文 *
QuEChERS-超高效液相色谱-QDa质谱法快速测定白菜与油菜中15种氨基甲酸酯类农药及代谢物残留;王纯强;钱永忠;章程辉;邱静;;农药学学报(第04期);全文 *
RP-HPLC法检测化妆品中奎宁的含量;陈志蓉;刘洋;张鹏祥;赵华;;中国药事(第09期);全文 *
SIMULTANEOUS IDENTIFICATION AND QUANTIFICATION OF HYDROQUINONE, TRETINOIN AND BETAMETHASONE IN COSMETIC PRODUCTS BY ISOCRATIC REVERSED PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY;BAITHA PALANGGATAN MAGGADANI等;IInntteerrnnaattiioonnaall JJoouurrnnaall ooff AApppplliieedd PPhhaarrmmaacceeuuttiiccs;20191231;第11卷(第3期);全文 *
中国第6次总膳食调查样品中杀螨剂的含量及暴露分析;辛少鲲;赵晓雪;吕冰;陈达炜;李敬光;赵云峰;吴永宁;;卫生研究(第03期);全文 *
刘华良 ; 杨润 ; 李放 ; 马永建 ; .化妆品中7种常见抗生素的超高效液相色谱测定法.环境与健康杂志.2009,(第05期),全文. *
化妆品中7种常见抗生素的超高效液相色谱测定法;刘华良;杨润;李放;马永建;;环境与健康杂志(第05期);全文 *
应用液质联用技术测定化妆品中12种磺胺类药物;曹红;王浩;刘艳琴;杨红梅;郭启雷;;日用化学工业(第04期);全文 *
曹红 ; 王浩 ; 刘艳琴 ; 杨红梅 ; 郭启雷 ; .应用液质联用技术测定化妆品中12种磺胺类药物.日用化学工业.2010,(第04期),全文. *
液相色谱-串联质谱法同时检测膏霜类化妆品中的41种禁用抗感染药物;汪鑫;陈蓉;;中国药师(第08期);全文 *
液相色谱-串联质谱法同时测定化妆品中18种磺胺类相关化合物残留;钟吉强;郑荣;简龙海;刘畅;王柯;;香料香精化妆品(第06期);全文 *
王纯强 ; 钱永忠 ; 章程辉 ; 邱静 ; .QuEChERS-超高效液相色谱-QDa质谱法快速测定白菜与油菜中15种氨基甲酸酯类农药及代谢物残留.农药学学报.2018,(第04期),全文. *
祛痘类化妆品中3种禁用除螨剂的高效液相色谱检测及质谱确证;郭项雨;李晶瑞;马强;孟宪双;白桦;;分析试验室(第09期);全文 *
超高效液相色谱一串联质谱法测定10种食品中的阿维菌素类药物残留;张文娟;连庚寅;郭晓喜;杨小兰;宋欢;食品科学;第33卷(第018期);全文 *
辛少鲲 ; 赵晓雪 ; 吕冰 ; 陈达炜 ; 李敬光 ; 赵云峰 ; 吴永宁 ; .中国第6次总膳食调查样品中杀螨剂的含量及暴露分析.卫生研究.2020,(第03期),全文. *
钟吉强 ; 郑荣 ; 简龙海 ; 刘畅 ; 王柯 ; .液相色谱-串联质谱法同时测定化妆品中18种磺胺类相关化合物残留.香料香精化妆品.2014,(第06期),全文. *
高效液相色谱-串联质谱法检测茶青中124种农药残留;祝愿;李俊;蔡滔;庞宏宇;王艺蓉;杨亚;周雪丽;刘凯;罗华兰;王震;杜楠;;食品安全质量检测学报;20190425(第08期);全文 *
高效液相色谱法测定化妆品中的乐杀螨和克螨特含量;顾宇翔;熊薇;戴彦韵;;香料香精化妆品;20151030(第05期);全文 *
高效液相色谱-质谱联用法快速筛查化妆品中112 种禁用药物;陈少波等;《分析测试学报》;第37卷(第11期);摘要以及第1~3节 *

Also Published As

Publication number Publication date
CN115267011A (en) 2022-11-01

Similar Documents

Publication Publication Date Title
Santos-Fandila et al. Quantitative determination of neurotransmitters, metabolites and derivates in microdialysates by UHPLC–tandem mass spectrometry
CN104133006A (en) Method for detecting blood sugar-lowering and blood pressure-lowering drugs in blood by ultra high performance liquid-mass spectrometry
CN115267011B (en) Liquid chromatography-mass spectrometry chromatography method for qualitative detection of illegally added drugs in oil-control cosmetics
Klimenko et al. Validation of UV-spectrophotometric methods of quantitative determination in forensic and toxicological analysis: recovery
CN112782322A (en) Method for simultaneously determining 8 anti-tuberculosis drugs in human plasma based on LC-MS (liquid chromatography-Mass Spectrometry)
Kadam et al. Cassette analysis of eight beta-blockers in bovine eye sclera, choroid–RPE, retina, and vitreous by liquid chromatography–tandem mass spectrometry
Ortuño et al. Ion-selective electrode for the determination of some multidrug resistance reversers
CN109142593A (en) HPLC-DAD method measures Quetiapine drug concentration in human serum
CN106124682A (en) A kind of composition method of inspection of Radix Et Caulis Acanthopanacis Senticosi injection
Razeq et al. TLC–densitometry and UHPLC methods for simultaneous determination of amprolium HCl, ethopabate, and sulfaquinoxaline-Na in their new combined dosage form
Morelli Determination of ternary mixtures of vitamins by ratio-spectra zero-crossing derivative spectrophotometry
CN105987965A (en) Method for determining various types of abuse drugs in human whole blood
Campanella et al. Determination of cholic acids by ion selective liquid membrane electrode in pharmaceutical products
CN106596750B (en) Six kinds of content assaying methods in relation to substance in a kind of otoginsenoside preparation of sodium
CN113933418A (en) Method for simultaneously detecting concentrations of 7 antibiotic drugs in human serum
Shpigun et al. Flow-injection method of spectrophotometric determination of catecholamines in pharmaceutical formulations
Walash et al. Spectrophotometric determination of rifampin in the presence of its degradation products in pharmaceutical preparations
CN113624880B (en) High-throughput screening method for residual medicines in honey
De Alwis et al. Determination of erythromycin in medicated salmonid fish feed by liquid chromatography and UV spectroscopy
CN111044630B (en) Method for analyzing metabolic pathway change by tear metabonomics for xerophthalmia and application thereof
CN115236222B (en) Method for detecting human epidermal growth factor in cosmetics
CN106814049A (en) A kind of Capillary Electrophoresis vivo detection method of Cobratoxin
CN107748216B (en) The detection method of 4 kinds of functional active components in a kind of Rapid Simultaneous Determination YEDAO LUGUI JIU
Sidelnikov RESEARCH OF BIOLOGICALLY ACTIVE COMPOUNDS ABILITY TO DIFFUSE THROUGH THE GASTROINTESTINAL TRACT WALL USING PARALLEL ARTIFICIAL MEMBRANES
CN113866299A (en) Method for detecting neurotransmitter in dialysate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant