CN108132309B - An analytical method for determining the residual amount of copper in Dendrobium officinale - Google Patents
An analytical method for determining the residual amount of copper in Dendrobium officinale Download PDFInfo
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- 241001076416 Dendrobium tosaense Species 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims abstract description 30
- 238000004458 analytical method Methods 0.000 title claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 238000007865 diluting Methods 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001212 derivatisation Methods 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010812 external standard method Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000004704 ultra performance liquid chromatography Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000004949 mass spectrometry Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 abstract description 3
- 239000002207 metabolite Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000002452 interceptive effect Effects 0.000 abstract description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 abstract description 2
- ATWQTGLWGFGTRE-UHFFFAOYSA-N copper;thiadiazole Chemical compound [Cu].C1=CSN=N1 ATWQTGLWGFGTRE-UHFFFAOYSA-N 0.000 abstract 2
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical compound SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000001946 ultra-performance liquid chromatography-mass spectrometry Methods 0.000 description 3
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 2
- 244000241235 Citrullus lanatus Species 0.000 description 2
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 2
- 208000031888 Mycoses Diseases 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005940 Thiacloprid Substances 0.000 description 2
- 241000605118 Thiobacillus Species 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000447 pesticide residue Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 1
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 1
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 1
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical group 0.000 description 1
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明提供一种测定铁皮石斛中噻菌铜残留量的方法，在铁皮石斛样品中加入硫化钠溶液，噻菌铜衍生转化成代谢产物噻二唑，乙腈提取后加酸调节pH值，再加入乙酸乙酯液液分配，取有机相用旋转蒸发器浓缩至干，利用固相萃取法去除提取液中干扰物质，最后采用超高效液相色谱‑质谱/质谱联用仪检测。本发明方法可以有效避免样品的基质干扰，获得良好的效果。本发明方法具有较高的准确度，精密度和灵敏度，回收率高，杂质干扰小可以有效的测定噻菌铜在铁皮石斛中的含量。
The invention provides a method for determining the residual amount of thiadiazole copper in Dendrobium officinale. Sodium sulfide solution is added to a sample of Dendrobium officinale, the thiadiazole copper is derivatized and converted into a metabolite thiadiazole, after extraction with acetonitrile, acid is added to adjust the pH value, and then add Ethyl acetate was liquid-liquid distributed, and the organic phase was concentrated to dryness with a rotary evaporator, and the interfering substances in the extract were removed by solid-phase extraction, and finally detected by ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry. The method of the present invention can effectively avoid the matrix interference of the sample and obtain good results. The method of the invention has high accuracy, precision and sensitivity, high recovery rate and little interference of impurities, and can effectively determine the content of thiophanate copper in Dendrobium officinale.
Description
Technical Field
The invention belongs to the technical field of pesticide residue determination, and particularly relates to an analysis method for the residual quantity of thiediazole copper in dendrobium officinale.
Background
Thiacloprid is a patent product developed by chemical Limited company of Longwan of Zhejiang, has the chemical name of 2-amino-5-mercapto-1, 3 and 4-thiadiazole copper complex, and the main metabolite is thiadiazole, so that the thiadiazol copper complex is an efficient and broad-spectrum systemic bactericide. The bactericidal mechanism is unique, the thiazole group has unique prevention effect on bacteria, and the copper ions have prevention and treatment effects on fungi and bacteria, and can be widely used for preventing and treating more than 20 kinds of crops with more than 60 kinds of bacteria and fungal diseases. At present, the pesticide composition is applied to the prevention and treatment of diseases such as soft rot, leaf spot, bacterial blight and the like on crops such as Chinese cabbages, tomatoes, oranges, cucumbers, rice, watermelons, tobaccos and the like. The pesticide has high efficiency, low toxicity and safety, has high efficiency in preventing and treating bacterial and fungal diseases of crops, and has obvious effect in preventing and treating soft rot of dendrobium officinale.
At present, no corresponding national and industrial standards exist for a method for detecting the residual Thiodiazole copper. In recent years, domestic literature reports that the high performance liquid chromatography is adopted to measure the residual quantity of Thiobacillus copper in watermelon, soil and tobacco. Because the matrix of the dendrobium officinale is complex, the high performance liquid chromatography method is adopted for detection, the purification effect is not ideal, the matrix interference is serious, the sensitivity is low, the residual quantity of the thiediazole copper in the dendrobium officinale cannot be accurately measured by using the liquid phase method, and a more effective detection method needs to be developed.
Disclosure of Invention
In order to evaluate the safety of the thiediazole copper in the dendrobium officinale, the invention establishes a method for determining the residual quantity of the thiediazole copper in the dendrobium officinale by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC/MS/MS) method. Adding a sodium sulfide solution into a dendrobium officinale sample, deriving and converting thiodiazole copper into a metabolite thiadiazole, extracting acetonitrile, adding acid to adjust the pH value, adding ethyl acetate for liquid-liquid distribution, taking an organic phase, concentrating the organic phase to dryness by using a rotary evaporator, removing interfering substances in an extracting solution by using a solid phase extraction method, and finally detecting by using an ultra performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC/MS/MS). The results show that: the linear range of the method is 0.05-5.0 mg/L, the lowest detection concentration is 0.050 mg/kg, and the average recovery rate is 92-96%. The invention provides the following technical scheme:
an analysis method for determining the residual quantity of thiediazole copper in dendrobium officinale, which is characterized by comprising the following steps:
(1) derivatization: weighing 5-10g of sample, placing the sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 30-60 ℃, and oscillating for 30 minutes;
(2) extraction: adding 20-60 mL of acetonitrile, oscillating at room temperature for 1-2 hours, filtering after oscillation is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 50-100 mL ethyl acetate for extraction, taking an upper organic phase, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument.
The specific method for determining the residual quantity of thiediazole copper in the dendrobium officinale comprises the following steps:
1. test materials
Reagents and materials: sodium sulfide, dimethylformamide, ethyl acetate, acetone, petroleum ether were all analytical, methanol (chromatographic purity, Merck, Germany), pure water (Millipore Co., Ltd.), Flori silica solid phase column (Beijing vibrato science and technology Co., Ltd.)
And (3) standard substance: thiacloprid standard (purity 99.1%, provided by Longwan chemical Co., Ltd., Zhejiang)
The instrument comprises the following steps: shimadzu LCMS8050 high performance liquid chromatography tandem mass spectrometer; shanghai Shensheng R-201 type rotary evaporator; shanghai Shensheng W201B model digital control constant temperature bath kettle; model SHZ-d (iii) circulating water vacuum pump; an SPS202F model electronic balance; one ten thousandth day of METTLER TOLEDO, switzerland.
2. Test method
Derivative extraction: weighing 5.0g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20 mL of 0.1mol/L sodium sulfide solution, heating to 30 ℃, oscillating for 30 minutes, adding 20.0 mL of acetonitrile, continuing oscillating for 1 hour, performing suction filtration after oscillation is finished, performing suction filtration, and using 1mol/L H as filtrate2SO4Adjusting pH to 4-5, transferring the above solution to a separating funnel, adding 50 mL ethyl acetate for extraction, collecting upper organic phase, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in 40 deg.C constant temperature water bath to near dry, adding 2.0 mL petroleum ether and acetone (1:)1, v: v) dissolving, and purifying.
Purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure in a constant temperature water bath at 40 deg.C until dry, blowing with nitrogen, diluting with chromatographic methanol to desired volume, and filtering with 0.22 μm filter membrane.
3. Conditions of instrumental analysis
3.1 liquid phase conditions
A chromatographic column: waters acquity UPLCTM BEH C18（1.7µm，2.1×100 mm）；
Column temperature: 40 ℃;
flow rate: 0.20 mL/min;
mobile phase: acetonitrile: 0.1% aqueous formic acid =20:80 (v/v)
Sample introduction amount: 1 mu L;
quantification by external standard method.
3.2 Mass Spectrometry conditions
Mass spectrometer conditions: capillary voltage is 4.0 kV, DL temperature is 250 ℃, atomizing gas flow is 3.0L/min, Interface temperature is 300 ℃, heater flow is 10L/min, ionization mode: ESI+The detection mode is multi-reaction monitoring scan mode (MRM), see table 1.
TABLE 1 Mass Spectrometry conditions
| Parent ion | Daughter ions | Q1 Pre Bias(V) | CE(V) | Q3 Pre Bias(V) |
| 133.90 | 75.00 | -14 | -17 | -16 |
| 133.90 | 42.95 | -24 | -31 | -17 |
4. Linear relation of method
And dissolving the standard sample by using dimethylformamide to prepare a 100 mg/L standard stock solution of the thiediazole copper. Diluting with dimethylformamide to obtain the standard working solutions of Thiobacillus copper series with concentrations of 0.05, 0.10, 0.20, 0.50, 1.0, 2.0 and 5.0 mg/L. Adding a series of working solutions with the sample injection concentration of 0.05, 0.10, 0.20, 0.50, 1.0, 2.0 and 5.0 mg/L into blank water, injecting according to the processing steps and instrument conditions of the method, drawing a standard curve of the thiediazole copper by using concentration-peak area, wherein the regression equation is y = 287604x-5164, R = 0.9995, wherein y is the area of the thiediazole copper peak, and x is the concentration of the standard solution.
5. Method recovery and relative standard deviation
In the blank dendrobium officinale samples, 3 levels of concentration (0.050, 0.50 and 10 mg/kg) of thiediazole copper standard solutions are respectively added, each level is repeated for 5 times, meanwhile, the 3 levels of concentration of thiediazole copper standard solutions are added into the blank aqueous solution to be used as standard solution for treatment, sample injection is carried out according to the treatment steps and the instrument method, the recovery rate is measured, the result is shown in table 2, and the recovery rate curve is shown in fig. 2. Experiments show that the recovery rate meets the detection requirement of pesticide residue, and the method is proved to have better recovery rate and repeatability.
TABLE 2 Thiodiazole copper addition recovery test
6. Minimum detected concentration of the method
By applying the method, the minimum addition concentration of the thiediazole copper in the dendrobium officinale is 0.050 mg/kg, and the response values of samples on the instrument are all larger than 3 times of the signal-to-noise ratio of the instrument, so that the following results are obtained: the lowest detection concentration of the thiediazole copper in the dendrobium officinale is 0.050 mg/kg.
7. Minimum detected amount
Under the above analysis conditions, the minimum detection amount of Thiodiazole copper by the instrument is 5.0X 10-11g. Taking the 3 times signal-to-noise ratio of the instrument as the detection limit of the instrument, and taking the minimum detection amount (g) = detection limit (mg/L) × sample injection volume (muL) × 10-9。
The analysis method for determining the residual quantity of the thiediazole copper in the dendrobium officinale provided by the invention has the positive effects that: the method can effectively avoid the matrix interference of the sample and obtain good effect. The method has the advantages of high accuracy, precision, sensitivity, high recovery rate and small impurity interference, and can effectively determine the content of the thiediazole copper in the dendrobium officinale.
Drawings
FIG. 1 is a chromatogram of a blank Dendrobium officinale sample without Thiodiazole copper.
FIG. 2 is a chromatogram of a blank Dendrobium officinale sample added with 0.50 mg/kg Thiodiazole copper.
Detailed Description
To more fully explain the implementation of the present invention, an example of an analysis method for the residual amount of thiediazole copper in dendrobium officinale is provided. These examples are merely illustrative and do not limit the scope of the invention. All of which are commercially available.
Example 1
(1) Derivatization: weighing 5g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20 mL of 0.1mol/L sodium sulfide solution, heating to 30 ℃, and oscillating for 30 minutes;
(2) extraction: then 20 mL of acetonitrile is added, the mixture is shaken for 1 hour at room temperature, after shaking, the mixture is filtered, and the filtrate is used at the concentration of 1mol/L H2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 50 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be lower than 0.050 mg/kg through the steps.
Example 2
(1) Derivatization: weighing 10g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 60 mL of 0.1mol/L sodium sulfide solution, heating to 60 ℃, and oscillating for 30 minutes;
(2) extraction: adding 60 mL of acetonitrile, shaking at room temperature for 2 hours, filtering after shaking is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 100 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be 0.081 mg/kg through the steps.
Example 3
(1) Derivatization: weighing 7.5 g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 40 ℃, and oscillating for 30 minutes;
(2) extraction: then 40 mL of acetonitrile is added, the mixture is shaken at room temperature for 1.5 hours, after shaking, the mixture is filtered, and the filtrate is used at the concentration of 1mol/L H2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 70 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be lower than 0.050 mg/kg through the steps.
It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments without departing from the scope and spirit of the invention, and it is intended that all such changes and modifications as fall within the true spirit and scope of the invention be interpreted in accordance with the principles of the invention. And the invention is not limited by the example embodiments set forth in the description.
Claims (1)
1. An analysis method for determining residual quantity of thiediazole copper in dendrobium officinale, which is characterized by comprising the following steps:
(1) derivatization: weighing 5-10g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 30-60 ℃, and oscillating for 30 min;
(2) extraction: adding 20-60 mL of acetonitrile, oscillating at room temperature for 1-2 hours, filtering after oscillation is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: and (2) transferring the solution to a separating funnel, adding 50-100 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate at a constant temperature of 40 ℃ under reduced pressure until the filtrate is nearly dry, and adding 2.0 mL of petroleum ether: acetone, v: v = 1: 1, dissolved, ready to be purified;
(4) purifying: taking a Florisil solid phase column, activating petroleum ether, taking the extract to be purified, and sampling the extract, namely petroleum ether, acetone, v: v = 1: 1, eluting, collecting eluate, concentrating under reduced pressure to dry, blowing dry with nitrogen, diluting to constant volume with methanol, and filtering with filter membrane;
(5) and (3) determination: detecting by adopting a liquid chromatography-mass spectrometer, wherein the determination conditions are as follows: a chromatographic column: waters acquity UPLCTM BEH C18, 1.7 μm, 2.1 × 100 mm; column temperature: 40 ℃; flow rate: 0.20 mL/min; mobile phase: acetonitrile: 0.1% aqueous formic acid =20:80, v/v; sample introduction amount: 1 mu L; quantifying by an external standard method; mass spectrum conditions: the capillary voltage is 4.0 kV, the DL temperature is 250 ℃, the atomizing gas flow is 3.0L/min, the Interface temperature is 300 ℃, and the heater flow is 10L/min; an ionization mode: ESI+The detection mode is a multi-reaction monitoring scanning mode, and the quantitative and qualitative ion pair is 133.90>75.00, quant Q1-17V; CE-17V; Q3-16V, 133.90>42.95, qualitative Q1-24V; CE-31V; Q3-17V.
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