CN110243990A - The measuring method of illegal additive in a kind of cosmetics - Google Patents
The measuring method of illegal additive in a kind of cosmetics Download PDFInfo
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- CN110243990A CN110243990A CN201910664136.5A CN201910664136A CN110243990A CN 110243990 A CN110243990 A CN 110243990A CN 201910664136 A CN201910664136 A CN 201910664136A CN 110243990 A CN110243990 A CN 110243990A
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- G—PHYSICS
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- 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
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- 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
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
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Abstract
The invention discloses the quick test for identification technologies of additive illegal in a kind of cosmetics based on ionization in situ-super-resolution Mass Spectrometer Method and cloud search strategy.Once screening goes out illegal additive, respective standard product are found, parallel reaction monitoring pattern can be used for target compound and carry out fast quantitative analysis.The present invention mainly includes data acquisition and data processing two large divisions.The versatility and validity of method greatly improved in this method, make illegally to add detection technique and has risen to a new height, it is remarkably improved inspection working efficiency, to breaking through the too long technical bottleneck of round of visits, workflow duration be greatly shortened, push cosmetic science supervision, promote cosmetic industry to develop in a healthy way, ensures that cosmetics safety is of great significance.
Description
Technical field
The invention belongs to cosmetics detection technique fields, and in particular to one kind is not necessarily to illegal additive standard items, can examine
Survey the measuring method of the illegal additive in cosmetics.
Background technique
The detection of China's cosmetics at present is mainly according to " cosmetics safety technical specification " (version in 2015) and some countries
Standard, professional standard.These traditional standard methods are detected both for a certain or a kind of compound, and in practical work
In work, the problem of typically encountering is the illegal additive that do not know sample to be tested and may include, solution at this stage be by
Can inspection project all examines one time, this mode undoubtedly will cause the waste significantly of man power and material, and also it is different surely must
To satisfied result.Super-resolution mass spectrum including current most significant end remains on the screening for only paying close attention to target compound, only
It is to expand screening range, it is clear that do not give full play to the mass spectrographic advantage of super-resolution.It is another common problem encountered is that usually illegally adding
Add the content of object very high, the pollution of chromatography and mass spectrometer system is easily caused using liquid chromatograph mass spectrography, it is also possible to because of chromatography system
It unites missing inspection that is improper and causing determinand.The detection difficult point of illegal additive is not in detection sensitivity in cosmetics, and is
Its non-intellectual, screening do not have boundary, even if obtaining super-resolution mass spectrometric data, it is also not possible to manually parse to unknown chemical combination
Object makes identification.
Summary of the invention
The purpose of the present invention is to provide a kind of measuring method of additive illegal in cosmetics, data acquisition information is complete
It is whole, data retrieval is fast comprehensive, non-targeted compound can be detected in the case where no standard items.It solves at this stage only
The technical problem that target compound, recall rate are low, detection cycle is long can be detected.
To achieve the goals above, the invention adopts the following technical scheme:
The measuring method of illegal additive, step in a kind of cosmetics are as follows: sample extracts, screening measurement；The screening is surveyed
It surely include: data acquisition and data processing；
The sample extraction step are as follows: weigh 0.5g sample, in 15mL centrifuge tube, addition 1.0mL ethanol solution is set super
Ultrasound 5min in sound wave water-bath, vortex oscillation 10min, 10000r/min centrifugation 5min, takes supernatant 0.5mL to be transferred to 1.5mL
In plastic centrifuge tube, 0.5mL water is added, is vortexed and mixes, 10000r/min is centrifuged 5min, and gained sample solution is for measurement；
The positive ion mode of the Mass Spectrometry Conditions of the screening measurement are as follows: the source DART parameter: positive ion mode ionizes gas
Body is high-purity helium, and the flow velocity of helium is 3L/min, and gas ionization temperature is 500 DEG C；Using 12Dip-itSamplers mould
Formula sample introduction is drawn 1 μ L solution point with liquid-transfering gun and is placed on automatic sampling frame in glass bar lower end, sample rate 0.3mm/s, from
Component is exported away from mass spectrum import about 10mm；Q-Exative-orbitrap MS parameter: positively ionized FULL MS/DD-MS2Scanning
Mode；FullMS scanning range: m/z 100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow
Rate:7.00；AGC target:3e6；maximum IT:100ms；dd-MS2Scanning resolution: R=17500, AGC
target:2e5；maximum IT:60ms；NCE:20,40,60；
The negative ion mode of the Mass Spectrometry Conditions of the screening measurement are as follows: the source DART parameter: negative ion mode ionizes gas
Body is high-purity helium, and the flow velocity of helium is 3L/min, and gas ionization temperature is 500 DEG C；Using 12Dip-it Samplers mould
Formula sample introduction is drawn 1 μ L solution point with liquid-transfering gun and is placed on automatic sampling frame in glass bar lower end, sample rate 0.3mm/s, from
Component is exported away from mass spectrum import about 10mm；Q-Exative-orbitrap MS parameter: negative ionization FULL MS/DD-MS2Scanning
Mode；FullMS scanning range: m/z 100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow
Rate:7.00；AGC target:1e6；maximum IT:100ms；dd-MS2Scanning resolution: R=17500, AGC
target:2e5；maximum IT:60ms；NCE:20,40,60；
The collecting method are as follows: instrument cation and anion correcting fluid are corrected respectively first, quality
Number correction can be used by rear, then solution of materialsing, and respectively measurement is primary under negative ions mode under the Mass Spectrometry Conditions, often
Secondary sample introduction does two in parallel, and instrumental response value is within normal range (NR)；The instrument is Q-Exactive electrostatic orbit trap matter
Spectrometer, Direct Analysis in Real Time ion source DART SVP；
The data processing method are as follows: to the data of acquisition, handled using Compound Discoverer software, selection
MzCloud, Chemspider cloud database are retrieved, and are manually studied and judged to search result.
The illegal additive includes: 1388 disabling objects specified in 2015 editions " cosmetics safety technical specifications "
Matter.
The banned substance includes: hydrocortisone, clobetasol propionate, and Cimetidine, lincomycin, benzene sea are drawn
It is bright, one or more of betamethasone, Terbinafine, econazole.
The method for quantitatively determining that the screening measures for detecting chloramphenicol includes:
The source DART parameter: negative ion mode, ionized gas are high-purity helium, and the flow velocity of helium is 3L/min, gas from
Sonization temperature is 500 DEG C；Using 12Dip-it Samplers mode sample introduction, 1 μ L solution point is drawn under glass bar with liquid-transfering gun
End is placed on automatic sampling frame, and sample rate 0.3mm/s, ion source outlet is away from mass spectrum import about 10mm；
Q-Exative-orbitrap MS parameter: negative ionization FULL MS+PRM scan pattern；Scanning range: m/z
100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow rate:7.00；AGC target:1e6；
maximum IT:100ms；Parallel reaction monitoring pattern scanning resolution: R=17500, AGC target:2e5；maximum
IT:100ms；Ion, daughter ion and opposite collision energy are as follows: parent ion 321.0050, daughter ion 152.0353,121.0294,
NCE/% is 35；
The preparation of standard curve: standard addition method is used, 0.5g sample is weighed in 15mL centrifuge tube, appropriate standard is added
Stock solution is configured to the series standard sample that concentration is 0,2.0,5.0,10,20,50 and 100mg/L and presses after placing 30min
The extraction step operation, for mass spectroscopy；To measure chromatographic peak area as ordinate, corresponding concentration of standard solution is horizontal seat
Mark draws standard curve, asks regression equation and related coefficient；
Quantitative determination process: materials solution and corresponding standard solution make single-point or standard curve calibration, by external standard method,
With calculated by peak area.The response of drug should all be within the range of linearity that instrument detects in standard solution and sample solution；?
Under above-mentioned chromatographic condition, the chromatogram of standard solution, blank sample and addition sample is shown in attached drawing 1-3；
Blank test: in addition to sample is not added, operation repetitive is carried out using identical step；
Sample drug content is calculated by formula 1:
In formula:
X --- for the content of determinand in sample of having a try, unit mg/kg；
A --- the peak area of determinand in sample solution；
cs--- the concentration of determinand in standard solution, unit mg/L；
The constant volume of V --- sample solution, unit mL；
As--- the peak area of determinand in standard solution；
Sample mass representated by m --- sample solution, unit g；
Sensitivity: the determination of quantitative limit is determined according to the value of signal-to-noise ratio.Chloramphenicol mark is added in blank sample
Quasi- solution measures the ratio of its signal and noise, and as S/N >=10 and the rate of recovery and relative standard deviation meet cosmetics peace
Concentration when full code requirement is quantitative limit, and experimental result: the quantitative limit chloramphenicol of this method is 3mg/kg；
Accuracy: weighing 0.5g sample in 15mL centrifuge tube, appropriate Standard Stock solutions be added, and is configured to containing chloramphenicol
Concentration is the sample of 3.0,6.0 and 30mg/kg, and each concentration does 6 in parallel, after placing 30min, is handled by sample extraction method
After measure, calculate recovery of standard addition；Experimental result: recycling of this method on 3.0mg/kg~30mg/kg addition concentration level
Rate is 70%~120%；
Precision: weighing 0.5g sample in 15mL centrifuge tube, appropriate Standard Stock solutions be added, and is configured to containing chloramphenicol
Concentration is the sample of 3.0,6.0 and 30mg/kg, and each concentration does 6 in parallel, after placing 30min, is handled by sample extraction method
After measure, calculate indoor relative standard deviation；Experimental result: relative standard deviation≤15% in the laboratory of this method.
The utility model has the advantages that
It is non-in the cosmetics based on ionization in situ-super-resolution Mass Spectrometer Method and cloud search strategy the present invention is directed to study
The quick test for identification technology of method additive realizes really supper-fast, high-throughput, non-boundary screening.Once screening illegally adds out
Add object, find respective standard product, fast quantitative analysis is carried out for target compound using parallel reaction monitoring pattern.This method
Using open-and-shut pretreatment mode, the problem of being not necessarily to purification, and not will cause instrumental pollution.Ethyl alcohol extraction is adopted after being diluted with water
It is detected with DART- high resolution mass spectrum, ethyl alcohol is high to the extraction efficiency of determinand, is diluted with water the ionization that can improve the source DART
Efficiency improves sensitivity；The present invention mainly includes data acquisition and data processing two large divisions.First part is using straight in real time
Analysis ion source-super-resolution mass spectrum is connect, sample is not necessarily to chromatographic isolation through simple pre-treatment, direct injected, in more than ten seconds i.e.
Achievable data analysis and acquisition；Second part is to change the office of passing target detection using computer cloud retrieval technique
It is sex-limited, the comprehensive of the recall rate and data retrieval of illegal additive in cosmetics can be significantly improved.Existing method is all needle
The target detection of a kind of to certain or certain or even a few class compounds, if want complete detection antibiotics, glucocorticoids,
This several intermediate item of antiallergy class, antimycotic drug, will at least spend one week or more time, using ten come methods respectively into
Row detection, that also just for methodical project for, there are also some drugs to be not comprised in inside method, such as antifungal
In Terbinafine.This method handles the data of acquisition using Compound Discoverer software, selection mzCloud,
Chemspider database carries out cloud retrieval, and to search result from the mass deviation, matching degree and logic judgment of data
Aspect is manually studied and judged, and result is finally provided.
The versatility and validity of method greatly improved in this method, make illegally to add detection technique risen to one it is new
Level is remarkably improved inspection working efficiency, when to breaking through the too long technical bottleneck of round of visits, workflow is greatly shortened
It is long, cosmetic science supervision is pushed, cosmetic industry is promoted to develop in a healthy way, ensures that cosmetics safety is of great significance.
Currently, obtaining three articles by literature search.Document 1: chromatography 2016,35 (2) " Solid Phase Extraction/liquid phase color
The 53 kinds of glucocorticoids illegally added in spectrum-tandem mass spectrometry measurement facial mask class cosmetics "；Document 2: chromatography 2015,33 (3)
" Liquid Chromatography-Tandem Mass Spectrometry measures 25 kinds of quinolone drugs in cosmetics simultaneously "；Document 3: analysis test journal
2013,32 (3) " high performance liquid chromatography detects 12 kinds of taboo regulated substances in anti-acne class cosmetics simultaneously ".Comparing result see the table below
1。
Table 1: the application and three existing literature method comparing results
As shown in Table 1: the current detection in relation to Illegal addition in cosmetics is examined by classes of compounds
It surveys, and is all target detection, adaptability is not strong, and detection is only capable of covering a kind of compound every time, is not easy to find potential in cosmetics
Security risk.Illegally add in the cosmetics of this patent research ionization-super-resolution Mass Spectrometer Method in situ and cloud search strategy
Add object second test for identification technology, realizes really supper-fast, high-throughput, non-boundary screening.Passing target detection will be changed
Limitation not only significantly improves inspection working efficiency, is greatly shortened and examines workflow duration, and can significantly improve makeup
The recall rate of illegal additive in product has good market prospects and development trend.
Detailed description of the invention
Fig. 1 standard solution chromatogram (0,2,5,10,20,50,100mg/kg)
Fig. 2 adds sample chromatogram, and (mark-on is horizontal: 3.0mg/kg)
Fig. 3 blank sample chromatogram
(remarks: positive ordinate is the second order ms figure of sample to the Cimetidine second order ms figure detected in Fig. 4 sample 2, is born
Ordinate is the second order ms figure for composing library)
The diphenhydramine second order ms figure detected in Fig. 5 sample 3 (remarks are same as above)
The Terbinafine second order ms figure ((remarks are same as above) detected in Fig. 6 sample 4
The clobetasol propionate second order ms figure detected in Fig. 7 sample 1 and 5 (remarks are same as above)
Specific embodiment
The specific technical solution of the present invention described further below, in order to which those skilled in the art is further understood that
The present invention, without constituting the limitation to its right.
Embodiment 1
1 reagent and material
Reagent used below is analytical reagents in addition to especially indicating；Water is to meet level-one as defined in GB/T 6682
Water.
1.1 standard items: chloramphenicol (Chloramphenicol, No. CAS: 56-75-7), content is 99% or more.
1.2 ethyl alcohol: chromatographically pure.
1.3 isopropanols: chromatographically pure.
The preparation of 1.4 Standard Stock solutions: about each 25mg of chloramphenicol standard items is accurately weighed, is dissolved and is settled to methanol
50mL, being made into Standard Stock solutions concentration is 500mg/L.
2 instrument and equipments
2.1 Q-Exactive electrostatic Orbitrap mass spectrometers (Thermo Fisher company, the U.S.), Direct Analysis in Real Time from
Component DART SVP (Ion Sense company, the U.S.).
2.2 assay balances: sensibility reciprocal 0.00001g, Sartorius company.
2.3 balances: sensibility reciprocal 0.01g, Sartorius company.
2.4 vortex oscillators: MS 3basic, IKA company.
2.5 ultrasound baths: SW 30H, SONO SWISS company.
2.6 centrifuges: 3-30K, SIGMA company.
2.7 centrifuges: 1-14, SIGMA company.
3 determination steps
3.1 extracting
0.5g sample is weighed (accurately 1.0mL ethanol solution to be added and sets ultrasonic water in 15mL centrifuge tube to 0.01g)
Ultrasound 5min in bath, vortex oscillation 10min, 10000r/min are centrifuged 5min, take supernatant 0.5mL be transferred to 1.5mL plastics from
In heart pipe, 0.5mL water is added, is vortexed and mixes, 10000r/min is centrifuged 5min, for measurement.
3.2 measurement
3.2.1 screening measures
3.2.1.1 Mass Spectrometry Conditions
A) positive ion mode
The source DART parameter: positive ion mode, ionized gas are high-purity helium, and the flow velocity of helium is 3L/min, gas from
Sonization temperature is 500 DEG C；Using 12Dip-it Samplers mode sample introduction, 1 μ L solution point is drawn under glass bar with liquid-transfering gun
End is placed on automatic sampling frame, and sample rate 0.3mm/s, ion source outlet is away from mass spectrum import about 10mm.Q-Exative-
Orbitrap MS parameter: positively ionized FULL MS/DD-MS2Scan pattern；FullMS scanning range: m/z 100-1000；One
Grade full scan resolution ratio: R=70000；Sweep gas flow rate:7.00；AGC target:3e6；maximum IT:
100ms；dd-MS2Scanning resolution: R=17500, AGC target:2e5；maximum IT:60ms；NCE:20,40,60.
B) negative ion mode
The source DART parameter: negative ion mode, ionized gas are high-purity helium, and the flow velocity of helium is 3L/min, gas from
Sonization temperature is 500 DEG C；Using 12Dip-it Samplers mode sample introduction, 1 μ L solution point is drawn under glass bar with liquid-transfering gun
End is placed on automatic sampling frame, and sample rate 0.3mm/s, ion source outlet is away from mass spectrum import about 10mm.Q-Exative-
Orbitrap MS parameter: negative ionization FULL MS/DD-MS2Scan pattern；FullMS scanning range: m/z 100-1000；One
Grade full scan resolution ratio: R=70000；Sweep gas flow rate:7.00；AGC target:1e6；maximum IT:
100ms；dd-MS2Scanning resolution: R=17500, AGC target:2e5；maximum IT:60ms；NCE:20,40,60.
3.2.2 quantitative determination
3.2.2.1 Mass Spectrometry Conditions
To detect chloramphenicol, for being quantitative determined with chloramphenicol standard items.
The source DART parameter: negative ion mode, ionized gas are high-purity helium, and the flow velocity of helium is 3L/min, gas from
Sonization temperature is 500 DEG C；Using 12Dip-it Samplers mode sample introduction, 1 μ L solution point is drawn under glass bar with liquid-transfering gun
End is placed on automatic sampling frame, and sample rate 0.3mm/s, ion source outlet is away from mass spectrum import about 10mm.
Q-Exative-orbitrap MS parameter: negative ionization FULL MS+PRM scan pattern；Scanning range: m/z
100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow rate:7.00；AGC target:1e6；
maximum IT:100ms；Parallel reaction monitoring pattern (PRM) scanning resolution: R=17500, AGC target:2e5；
Maximum IT:100ms. parent ion, daughter ion and opposite collision energy are shown in Table 2.
The Mass Spectrometry Conditions of 2 chloramphenicol of table
Table 2 Mass spectral parameters ofChloramphenicol
Note: " * " is quota ion.
The preparation of 3.3 standard curves
Using standard addition method, 0.5g sample is weighed in 15mL centrifuge tube, appropriate Standard Stock solutions are added (can be step by step
Dilution), it is configured to the series standard sample that concentration is 0,2.0,5.0,10,20,50 and 100mg/L, after placing 30min, by institute
Extraction step operation is stated, for mass spectroscopy.To measure chromatographic peak area as ordinate, corresponding concentration of standard solution is horizontal seat
Mark draws standard curve, asks regression equation and related coefficient.
3.4 measuring method
3.4.1 screening measuring method
3.4.1.1 data acquire
Instrument cation and anion correcting fluid are corrected respectively first, mass number correction can make after passing through
With.
Materials solution, respectively measurement is primary under negative ions mode under above-mentioned Mass Spectrometry Conditions, each sample introduction do two it is flat
Row.Instrumental response value is within normal range (NR).
3.4.1.2 data processing
It to the data of acquisition, is handled using Compound Discoverer software, selects mzCloud, Chemspider etc.
Cloud database is retrieved, and is manually studied and judged to search result.
3.4.2 quantitative determination process
It materialses solution and corresponding standard solution, makees single-point or standard curve calibration, by external standard method, in terms of peak area
It calculates.The response of drug should all be within the range of linearity that instrument detects in standard solution and sample solution.In above-mentioned chromatostrip
Under part, the chromatogram of standard solution, blank sample and addition sample is shown in attached drawing.
3.4.2.1 blank test
In addition to sample is not added, operation repetitive is carried out using identical step.
3.4.2.2 result is calculated and is stated
Sample drug content is calculated by formula 1:
In formula:
X --- for the content of determinand in sample of having a try, unit is ng/kg (mg/kg)；
A --- the peak area of determinand in sample solution；
cs--- the concentration of determinand in standard solution, unit are micro- gram per liter (mg/L)；
The constant volume of V --- sample solution, unit are milliliter (mL)；
As--- the peak area of determinand in standard solution；
Sample mass representated by m --- sample solution, unit are gram (g).
3.4.2.3 method sensitivity, accuracy and precision
3.4.2.3.1 sensitivity
The determination of quantitative limit is determined according to the value of signal-to-noise ratio (S/N).Add chloramphenicol respectively in blank sample
With diphenhydramine standard solution, the ratio of its signal and noise is measured, as S/N >=10 and the rate of recovery and relative standard deviation are equal
Concentration when meeting cosmetics safety code requirement is quantitative limit.
Experimental result: the quantitative limit chloramphenicol of this method is 3mg/kg.
3.4.2.3.2 accuracy
0.5g sample is weighed in 15mL centrifuge tube, appropriate Standard Stock solutions (can dilute step by step) is added, is configured to contain
Chloramphenicol concentration is the sample of 3.0,6.0 and 30mg/kg, and each concentration does 6 in parallel, after placing 30min, by sample extraction side
It is measured after method processing, calculates recovery of standard addition.
Experimental result: this method 3.0mg/kg~30mg/kg addition concentration level on the rate of recovery be 70%~
120%.
3.4.2.3.3 precision
0.5g sample is weighed in 15mL centrifuge tube, appropriate Standard Stock solutions (can dilute step by step) is added, is configured to contain
Chloramphenicol concentration is the sample of 3.0,6.0 and 30mg/kg, and each concentration does 6 in parallel, after placing 30min, by sample extraction side
It is measured after method processing, calculates indoor relative standard deviation.
Experimental result: relative standard deviation≤15% in the laboratory of this method.
Embodiment 2
Method of the invention is used for routine testing, has detected cosmetic sample totally 100, detection chloramphenicol, lincomycin,
A variety of illegal additives such as clindamycin, Tinidazole, hydrocortisone, clobetasol propionate, diphenhydramine.
5 samples that conventional method is examined are verified using this method.Comparative result such as the following table 3 and specification is attached
Shown in Fig. 4-7:
3 sample verification result of table
In conclusion the use of this method, changes the limitation of passing target detection, can significantly improve non-in cosmetics
The recall rate of method additive.
Claims (4)
1. the measuring method of illegal additive in a kind of cosmetics, it is characterised in that step are as follows: sample extracts, screening measurement；Institute
Stating screening measurement includes: data acquisition and data processing；
The sample extraction step are as follows: weigh 0.5g sample, in 15mL centrifuge tube, 1.0mL ethanol solution is added and sets ultrasonic wave
Ultrasound 5min in water-bath, vortex oscillation 10min, 10000r/min centrifugation 5min, takes supernatant 0.5mL to be transferred to 1.5mL plastics
In centrifuge tube, 0.5mL water is added, is vortexed and mixes, 10000r/min is centrifuged 5min, and gained sample solution is for measurement；
The positive ion mode of the Mass Spectrometry Conditions of the screening measurement are as follows: the source DART parameter: positive ion mode, ionized gas are
High-purity helium, the flow velocity of helium are 3L/min, and gas ionization temperature is 500 DEG C；Using 12 Dip-it Samplers modes
Sample introduction is drawn 1 μ L solution point with liquid-transfering gun and is placed on automatic sampling frame in glass bar lower end, sample rate 0.3mm/s, ion
Source is exported away from mass spectrum import about 10mm；Q-Exative-orbitrap MS parameter: positively ionized FULL MS/DD-MS2Scan mould
Formula；FullMS scanning range: m/z 100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow rate:
7.00；AGC target:3e6；maximum IT:100ms；dd-MS2Scanning resolution: R=17500, AGC target:
2e5；maximum IT:60ms；NCE:20,40,60；
The negative ion mode of the Mass Spectrometry Conditions of the screening measurement are as follows: the source DART parameter: negative ion mode, ionized gas are
High-purity helium, the flow velocity of helium are 3L/min, and gas ionization temperature is 500 DEG C；Using 12 Dip-it Samplers modes
Sample introduction is drawn 1 μ L solution point with liquid-transfering gun and is placed on automatic sampling frame in glass bar lower end, sample rate 0.3mm/s, ion
Source is exported away from mass spectrum import about 10mm；Q-Exative-orbitrap MS parameter: negative ionization FULL MS/DD-MS2Scan mould
Formula；FullMS scanning range: m/z 100-1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow rate:
7.00；AGC target:1e6；maximum IT:100ms；dd-MS2Scanning resolution: R=17500, AGC target:
2e5；maximum IT:60ms；NCE:20,40,60；
The collecting method are as follows: instrument cation and anion correcting fluid are corrected respectively first, mass number school
Passing through rear can be used, then solution of materialsing, respectively measurement is primary under negative ions mode under the Mass Spectrometry Conditions, every time into
Sample does two in parallel, and instrumental response value is within normal range (NR)；The instrument is Q-Exactive electrostatic Orbitrap mass spectrometer,
Direct Analysis in Real Time ion source DART SVP；
The data processing method are as follows: to the data of acquisition, handled using Compound Discoverer software, selection
MzCloud, Chemspider cloud database are retrieved, and are manually studied and judged to search result.
2. measuring method as described in claim 1, it is characterised in that the illegal additive includes: 2015 editions " cosmetics
Technical specification of security " specified in 1388 banned substances.
3. measuring method as claimed in claim 2, it is characterised in that the banned substance includes: hydrocortisone, chlorine times
His rope propionic ester, Cimetidine, lincomycin, diphenhydramine, one or more of betamethasone, Terbinafine, econazole.
4. measuring method as described in claim 1, it is characterised in that the screening measurement is determined for detecting chloramphenicol
Quantity measuring method includes:
The source DART parameter: negative ion mode, ionized gas are high-purity helium, and the flow velocity of helium is 3L/min, gas ionization
Temperature is 500 DEG C；Using 12 Dip-it Samplers mode sample introductions, 1 μ L solution point is drawn in glass bar lower end with liquid-transfering gun
It is placed on automatic sampling frame, sample rate 0.3mm/s, ion source outlet is away from mass spectrum import about 10mm；
Q-Exative-orbitrap MS parameter: negative ionization FULL MS+PRM scan pattern；Scanning range: m/z 100-
1000；Level-one full scan resolution ratio: R=70000；Sweep gas flow rate:7.00；AGC target:1e6；
maximum IT:100ms；Parallel reaction monitoring pattern scanning resolution: R=17500, AGC target:2e5；maximum
IT:100ms；Ion, daughter ion and opposite collision energy are as follows: parent ion 321.0050, daughter ion 152.0353,121.0294,
NCE/% is 35；
The preparation of standard curve: standard addition method is used, 0.5g sample is weighed in 15mL centrifuge tube, appropriate standard inventory is added
Solution is configured to the series standard sample that concentration is 0,2.0,5.0,10,20,50 and 100mg/L, after placing 30min, by described
Extraction step operation, for mass spectroscopy；To measure chromatographic peak area as ordinate, corresponding concentration of standard solution is abscissa,
Standard curve is drawn, regression equation and related coefficient are asked；
Quantitative determination process: materials solution and corresponding standard solution make single-point or standard curve calibration, by external standard method, with peak
Areal calculation.The response of drug should all be within the range of linearity that instrument detects in standard solution and sample solution；
Blank test: in addition to sample is not added, operation repetitive is carried out using identical step；
Sample drug content is calculated by formula 1:
In formula:
X --- for the content of determinand in sample of having a try, unit mg/kg；
A --- the peak area of determinand in sample solution；
cs--- the concentration of determinand in standard solution, unit mg/L；
The constant volume of V --- sample solution, unit mL；
As--- the peak area of determinand in standard solution；
Sample mass representated by m --- sample solution, unit g；
Sensitivity: the determination of quantitative limit is determined according to the value of signal-to-noise ratio.It is molten that chloramphenicol standard is added in blank sample
Liquid measures the ratio of its signal and noise, and as S/N >=10 and the rate of recovery and relative standard deviation meet cosmetics safety rule
Concentration when model requires is quantitative limit, and experimental result: the quantitative limit chloramphenicol of this method is 3mg/kg；
Accuracy: weighing 0.5g sample in 15mL centrifuge tube, appropriate Standard Stock solutions be added, and is configured to containing chloramphenicol concentration
For the sample of 3.0,6.0 and 30mg/kg, each concentration is done 6 in parallel, after placing 30min, is surveyed after handling by sample extraction method
It is fixed, calculate recovery of standard addition；Experimental result: this method adds the rate of recovery on concentration level in 3.0mg/kg~30mg/kg and is
70%~120%；
Precision: weighing 0.5g sample in 15mL centrifuge tube, appropriate Standard Stock solutions be added, and is configured to containing chloramphenicol concentration
For the sample of 3.0,6.0 and 30mg/kg, each concentration is done 6 in parallel, after placing 30min, is surveyed after handling by sample extraction method
It is fixed, calculate indoor relative standard deviation；Experimental result: relative standard deviation≤15% in the laboratory of this method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112345710A (en) * | 2020-12-16 | 2021-02-09 | 吉林大学珠海学院 | Sampling device for identifying, detecting and analyzing forbidden substances in cosmetics |
| CN113899837A (en) * | 2021-08-31 | 2022-01-07 | 广州海关技术中心 | High-flux non-targeted screening method for pollutants in regenerated PET (polyethylene terephthalate) material for food contact |
| CN114047280A (en) * | 2021-10-21 | 2022-02-15 | 苏州药明康德新药开发有限公司 | Method for detecting content of non-volatile unknown substances in medical instrument leaching liquor |
| CN114088646A (en) * | 2021-11-17 | 2022-02-25 | 汕头海关技术中心 | Method for rapidly identifying illegal cosmetic additives |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103278557A (en) * | 2013-04-10 | 2013-09-04 | 江苏康缘药业股份有限公司 | Method for quantitative analysis of drug by using non surface-contact atmospheric pressure ionization/quadrupole-flight time mass-spectrometric technique |
| CN103389350A (en) * | 2013-08-09 | 2013-11-13 | 中国检验检疫科学研究院 | Method for measuring chloramphenicol antibiotics in cosmetics |
| CN103760219A (en) * | 2014-01-16 | 2014-04-30 | 江苏康缘药业股份有限公司 | Method for analyzing and identifying different phenolic acid components in resina draconis based on DART/Q-TOF method |
| CN105865885A (en) * | 2016-04-06 | 2016-08-17 | 中国计量科学研究院 | Quick screening method for chloramphenicol in honey matrix |
| CN107543890A (en) * | 2017-03-29 | 2018-01-05 | 中国检验检疫科学研究院 | The screening method of chloromycetin series antibiotics chemical risk material in a kind of washing product |
| CN107831210A (en) * | 2017-12-19 | 2018-03-23 | 威海出入境检验检疫局检验检疫技术中心 | The surface ionizing high resolution mass spectrum detection method of Isolated From Thymelaeaceae Species disabling composition in a kind of cream kind cosmetics |
| CN107898667A (en) * | 2017-11-14 | 2018-04-13 | 北京工商大学 | A kind of method that the skin care compositions suitable for sensitive skin is prepared based on skin lipid group |
| CN108020591A (en) * | 2016-11-03 | 2018-05-11 | 北京出入境检验检疫局检验检疫技术中心 | The detection method of illegal additive in a kind of Direct Analysis in Real Time ion gun-high resolution mass spectrum combination examination slimming health food |
| CN108169315A (en) * | 2017-12-19 | 2018-06-15 | 北京出入境检验检疫局检验检疫技术中心 | Surface ionizing-high resolution mass spectrum detection method of bloodroot disabling ingredient in a kind of liquid type cosmetics |
-
2019
- 2019-07-23 CN CN201910664136.5A patent/CN110243990A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103278557A (en) * | 2013-04-10 | 2013-09-04 | 江苏康缘药业股份有限公司 | Method for quantitative analysis of drug by using non surface-contact atmospheric pressure ionization/quadrupole-flight time mass-spectrometric technique |
| CN103389350A (en) * | 2013-08-09 | 2013-11-13 | 中国检验检疫科学研究院 | Method for measuring chloramphenicol antibiotics in cosmetics |
| CN103760219A (en) * | 2014-01-16 | 2014-04-30 | 江苏康缘药业股份有限公司 | Method for analyzing and identifying different phenolic acid components in resina draconis based on DART/Q-TOF method |
| CN105865885A (en) * | 2016-04-06 | 2016-08-17 | 中国计量科学研究院 | Quick screening method for chloramphenicol in honey matrix |
| CN108020591A (en) * | 2016-11-03 | 2018-05-11 | 北京出入境检验检疫局检验检疫技术中心 | The detection method of illegal additive in a kind of Direct Analysis in Real Time ion gun-high resolution mass spectrum combination examination slimming health food |
| CN107543890A (en) * | 2017-03-29 | 2018-01-05 | 中国检验检疫科学研究院 | The screening method of chloromycetin series antibiotics chemical risk material in a kind of washing product |
| CN107898667A (en) * | 2017-11-14 | 2018-04-13 | 北京工商大学 | A kind of method that the skin care compositions suitable for sensitive skin is prepared based on skin lipid group |
| CN107831210A (en) * | 2017-12-19 | 2018-03-23 | 威海出入境检验检疫局检验检疫技术中心 | The surface ionizing high resolution mass spectrum detection method of Isolated From Thymelaeaceae Species disabling composition in a kind of cream kind cosmetics |
| CN108169315A (en) * | 2017-12-19 | 2018-06-15 | 北京出入境检验检疫局检验检疫技术中心 | Surface ionizing-high resolution mass spectrum detection method of bloodroot disabling ingredient in a kind of liquid type cosmetics |
Non-Patent Citations (6)
| Title |
|---|
| MANUELA HAUNSCHMIDT ET AL: "Identification and semi-quantitative analysis of parabens and UV filters in cosmetic products by direct-analysis-in-real-time mass spectrometry and gas chromatography with mass spectrometric detection", 《ANALYTICAL METHODS》 * |
| QIANG MA ET AL: "Direct Identification of Prohibited Substances in Cosmetics and Foodstuffs Using Ambient Ionization on a Miniature Mass Spectrometry System", 《ANAL CHIM ACTA.》 * |
| XIU QIN LI ET AL: "Rapid quantification of trace chloramphenicol in honey under ambient conditions using direct analysis via real-time QTRAP mass spectrometry", 《FOOD CHEMISTRY》 * |
| YANG ET AL: "Use of X500R QTOF for Monitoring of Additives in Cosmetics", 《HTTPS://ALGIMED.COM/PDF/SCIEX/X500/X500R/USE-OF-X500R-QTOF-FOR-MONITORING-OF-ADDITIVES-IN-COSMETICS.PDF》 * |
| 谷婕 等: "膏霜类化妆品中瑞香科植物禁用成分的表面离子化－高分辨质谱快速识别技术研究", 《分析仪器》 * |
| 黄晓娜 等: "基于DART-MS快速筛查面膜中的违禁组分的方法研究", 《河南省化学会2018年学术年会摘要集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112345710A (en) * | 2020-12-16 | 2021-02-09 | 吉林大学珠海学院 | Sampling device for identifying, detecting and analyzing forbidden substances in cosmetics |
| CN112345710B (en) * | 2020-12-16 | 2022-03-25 | 吉林大学珠海学院 | Sampling device for identifying, detecting and analyzing forbidden substances in cosmetics |
| CN113899837A (en) * | 2021-08-31 | 2022-01-07 | 广州海关技术中心 | High-flux non-targeted screening method for pollutants in regenerated PET (polyethylene terephthalate) material for food contact |
| CN114047280A (en) * | 2021-10-21 | 2022-02-15 | 苏州药明康德新药开发有限公司 | Method for detecting content of non-volatile unknown substances in medical instrument leaching liquor |
| CN114088646A (en) * | 2021-11-17 | 2022-02-25 | 汕头海关技术中心 | Method for rapidly identifying illegal cosmetic additives |
| CN114088646B (en) * | 2021-11-17 | 2024-04-12 | 汕头海关技术中心 | Method for rapidly identifying illegal additives of cosmetics |
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