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GB 23200.54-2016: Food safety national standard -- Determination of residual methacrylic acid ester fungicides in foodstuffs by gas chromatography-mass spectrometry
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Basic data

Standard ID GB 23200.54-2016 (GB23200.54-2016)
Description (Translated English) Food safety national standard -- Determination of residual methacrylic acid ester fungicides in foodstuffs by gas chromatography-mass spectrometry
Sector / Industry National Standard
Classification of Chinese Standard G25
Word Count Estimation 17,150
Date of Issue 2016-12-18
Date of Implementation 2017-06-18
Older Standard (superseded by this standard) SN/T 2237-2008
Regulation (derived from) State Health Commission, Ministry of Agriculture, Food and Drug Administration Notice No. 16 of 2016
Issuing agency(ies) National Health and Family Planning Commission of the People's Republic of China, State Food and Drug Administration

GB 23200.54-2016: Food safety national standard -- Determination of residual methacrylic acid ester fungicides in foodstuffs by gas chromatography-mass spectrometry


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Food safety national standard - Determination of residues methacrylic acid ester fungicide residues in foodstuffs by gas chromatography - mass spectrometry National Standard of the People 's Republic of China GB Instead of SN/T 2237-2008 National standards for food safety The amount of methacrylic acid ester fungicide in food Determination of gas chromatography - mass spectrometry National food safety standards- Determination of strobilurin fungicides residues in foods Gas chromatography-mass spectrometry 2016-12-18 release 2017-06-18 Implementation National Health and Family Planning Commission of the People 's Republic of China Issued by the Ministry of Agriculture of the People 's Republic of China State Administration of Food and Drug Administration

Foreword

This standard replaces SN/T 2237-2008 "Determination of Methoxy Acrylate Fungicide Residue in Import and Export Foods Gas Chromatography - Mass spectrometry ". Compared with SN/T 2237-2008, the main changes are as follows. - Standard text format is modified to national standard text format for food safety; - the name and scope of the "export food" to "food"; - increase the "other food reference implementation" in the standard range. This standard replaced the previous version of the standard release. -SN/T 2237-2008. National standards for food safety Determination of Residues of Methoxy Acrylate Fungicides in Food Gas chromatography - mass spectrometry

1 Scope

This standard specifies the preparation and determination of 11 kinds of methacrylic acid ester fungicide residues in foodstuffs (see Appendix A). This standard applies to apples, pears, grapes, cabbage, cucumbers, mushrooms, orange juice, tea drinks, rice, chestnut, beef, pork, chicken Meat, eggs and milk and other foods in the determination of 11 kinds of methacrylic acid ester fungicide residues. Including azoxystrobin, ketamine, pyrimethanone, (Z, E), oxime oxytetracycline, picolorate, pyrazole mushroom and oxytetracycline, other food Goods can refer to the implementation.

2 normative reference documents

The following documents are indispensable for the application of this document. For dated references, only the dated edition applies to this file. For undated references, the latest edition (including all modifications) applies to this document. GB 2763 National Standard for Food Safety - Maximum Residue Limit of Pesticides in Foodstuffs GB/T 6682 Analytical laboratory water specifications and test methods

3 principle

The samples were extracted with organic solvent and purified by gel permeation chromatography (GPC). After the eluate was concentrated and constant volume, the gas chromatographic mass spectrometer Determination of external standard method.

4 reagents and materials

Unless otherwise specified, all reagents are of analytical grade and water is in accordance with the primary water specified in GB/T 6682. 4.1 Reagents 4.1.1 Toluene (C7H8). Chromatographic pure. 4.1.2 Cyclohexane (C6H12). Chromatographic Purification. 4.1.3 Ethyl acetate (C4H8O2). Analytical purity. 4.1.4 acetonitrile (C2H3N). pure chromatography. 4.1.5 Methanol (CH4O). Chromatographic Purification. 4.1.6 Trichloromethane (CHCl3). analytical grade. 4.1.7 Sodium chloride (NaCl), analytical grade. 4.1.8 anhydrous sodium sulfate (Na2SO4), analytical grade. Before burning at 650 ℃ for 4h, placed in a dryer after cooling and standby. 4.2 solution preparation 4.2.1 Cyclohexane-ethyl acetate (1 1, V/V). Take 100 mL of cyclohexane, add 100 mL of ethyl acetate and shake well. 4.3 standards 4.3.1 Methoxy Acrylate Fungicides Standard Substance. See Appendix A. 4.4 standard solution preparation 4.4.1 Standard stock solution. accurately weighed fungicide standard 50 mg (accurate to 0.1 mg), dissolved in toluene, transferred to 50 mL brown Volumetric flask and constant volume to scale. The solution concentration was 1 mg/mL. -18 ℃ below the dark preservation, the shelf life of 12 months. 4.4.2 Standard Intermediate. Draw 1.00 mL. Standard stock solution, move into 100 ml. Brown volumetric flask, with cyclohexane - ethyl acetate volume, The solution concentration was 10 μg/mL. 0 ℃ ~ 4 ℃ dark preservation, the shelf life of 1 month. 4.4.3 standard working fluid. absorb a certain amount of standard intermediate, with cyclohexane - ethyl acetate diluted to the required concentration, the use of pre-preparation. 5 instruments and equipment. 5.1 Gas Chromatography Mass Spectrometer (GC-MS) with an electronically bombarded ion source (EI source). 5.2 Gel Chromatography Purification System (GPC). 5.3 Analysis of balance. 0.01 g and 0.0001 g. 5.4 Homogenizer. Maximum speed 20 000 r/min. 5.5 Centrifuge. Maximum speed 5 000 r/min. 5.6 Vortex Mixer. 5.7 chicken heart bottles. 100 mL. 5.8 Plastic centrifuge tube. 50 mL. 5.9 nitrogen blowing instrument.

6 Preparation and storage of samples

6.1 Preparation of the sample 6.1.1 Fruits and vegetables Extract about 500 g of fruit such as apple, mushroom, cucumber and other fruits or vegetables, cut it, and then use the crusher to process the sample into a slurry. Uniform, divided into two copies as a sample, into a clean sample bottle, sealed and marked. 6.1.2 Grains and nuts Extract rice and other nuts and chestnuts and other nut samples about 500 g, and then crushed by crusher and through the 2.0 mm round hole sieve, mix, Are divided into two as a sample, into the clean Sheng Sheng bag, sealed and marked. 6.1.3 meat and animal offal Extraction of beef, chicken, pork and other samples of about 500 g, chopped, with a crusher to sample processed into a slurry, mix, are divided into two As a sample, into a clean vial, sealed and marked. 6.1.4 Eggs Take the sample of about 500 g of eggs, peel the shell, and use the crusher to process the sample into a slurry, mix it, and divide it into two pieces. Clean the vials, sealed and marked. 6.1.5 Beverages and milk Take about 500 g of the beverage and milk samples, mix them into two pieces, and separate them into a clean sample vial. mark. Note. The above sample sampling site according to GB 2763 Appendix A implementation. 6.2 Sample storage Cereals, nuts and other samples stored at 0 ℃ ~ 4 ℃; fresh fruits, vegetables and meat, eggs, milk and beverages and other samples at -18 ℃ The following frozen storage. During the operation of the sample preparation, the sample should be protected from contamination or changes in the content of the residue.

7 Analysis steps

7.1 Extraction 7.1.1 samples of fruits, vegetables and beverages The prepared samples were thawed at room temperature and left for about 30 min. Weigh 15 g of the sample (accurate to 0.01 g) at 50 mL Plastic centrifuge tube, add 5g sodium chloride, vortex mixed 1 min, add 30 ml cyclohexane - ethyl acetate, and then vortex mixed 1 min, super Sonic extraction for 10 min, centrifuged at 4 000 r/min for 10 min. Take the supernatant to fill the funnel with 5 g of anhydrous sodium sulfate 20 mL of the filtrate (equivalent to 10 g of sample) into the heart of the bottle. 40 ℃ below the rotation concentrated to near dry. 7.1.2 Grain samples, nuts samples The prepared sample was removed and allowed to stand at room temperature for about 30 min. Weigh 15 g of the sample (accurate to 0.01 g) at 50 mL. plastic Centrifuge tube, add 5g sodium chloride, then add 30 ml of acetonitrile, vortex mixing 1 min, ultrasonic extraction 30 min, to 4 000 r/min Centrifuge for 10 min. Take the supernatant filled with 2g anhydrous sodium sulfate funnel, take 20 ml of filtrate (equivalent to 10 g sample) into the Heart of the bottle. 40 ℃ below the rotation concentrated to near dry. 7.1.3 Meat and animal offal The prepared samples were thawed at room temperature and left for about 30 min. Accurately weigh 15 g of the sample (accurate to 0.01 g) 50 mL of plastic centrifuge tube, add 5 g sodium chloride vortex mixed 1 min, standing 10 min, then add 30 mL of acetonitrile, ultrasonic extraction 30 min, Centrifuge at 4 000 r/min for 10 min. Take the supernatant filled with 5g anhydrous sodium sulfate funnel, take 20 ml of filtrate (equivalent to 10 g sample) into the heart of the bottle. 40 ℃ below the rotation concentrated to near dry. 7.1.4 eggs, milk samples The prepared samples were thawed at room temperature and left for about 30 min. Accurately weigh 10 g of the sample (accurate to 0.01 g) 50 ml of plastic centrifuge tube, add 5 ml of methanol, about 10 g of anhydrous sodium sulfate and 20 ml of chloroform, vortex mixing 1min, oscillation 20 min, centrifuged at 4 000 r/min for 10 min. The lower layer of chloroform was taken with a pipette and the residue was filled with 5 g of anhydrous sodium sulfate Bucket, collected in the heart of the chicken. Add 20 ml of trichloromethane and repeat the above steps for secondary extraction. Rinse the funnel with 20 ml of acetonitrile and water Sodium sulfate several times. Combined filtrate in the heart of the bottle, 40 ℃ below the water bath under reduced pressure to near dry. 7.2 Purification 7.2.1 The residue in the heart of the heart was dissolved in 4 mL of cyclohexane-ethyl acetate and transferred to a GPC vial for GPC purification. 7.2.2 GPC conditions. Bio beads (S-X3) gel purification column, the mobile phase of cyclohexane ethyl acetate, flow rate 4 mL/min, detection wave Long 254 nm. The injection volume was 2 mL. The eluate was collected from the 15 min to 20 min period, or the elution curve was taken according to the elution curve Determine the collection time period. 7.2.3 Concentration. The eluate collected in the heart of the heart was concentrated below 40 ° C to near dryness. 7.2.4 Dissolution. Dissolve the residue in the heart of the heart with 1.0 mL of cyclohexane-ethyl acetate and transfer to a GC vial for GC-MS detection. 7.3 Determination 7.3.1 Gas Chromatographic Analysis Reference Conditions A) Column. HP-5 ms quartz capillary column, 30 m × 0.25 mm (id), film thickness 0.25 μm, or equivalent; B) Column temperature program. 160 ° C for 1 min, rise to 280 ° C at 15 ° C/min for 4 min at 10 ° C/min Rose to 300 ° C for 10 min. C) Carrier gas flow rate. 0.8 mL/min for 10 min, 0.5 mL/min to 1.5 mL/min for 12 min; D) Inlet temperature. 280 ° C. E) mass spectrometer interface temperature. 280 ℃. F) Carrier gas. high purity helium, purity ≥99.999%. G) Injection method. no split injection, 1.5 min after the opening valve. H) Injection volume. 2.0 μL. I) GC-MS interface temperature. 280 ° C. 7.3.2 Reference conditions for mass spectrometry analysis A) Ionization mode. EI. B) Ionization energy. 70 eV. C) Quadrupole temperature. 150 ° C. D) ion source temperature. 230 ° C. E) Detection mode. Select ion mode (SIM). F) Monitoring of ions (m/z). 11 kinds of fungicides to choose the monitoring of ions in Table 1. G) solvent delay. 6 min. Table 1 11 kinds of fungicide retention time, qualitative and quantitative ions No. pesticide name Reference retention time / Min Quantitative ions M/z Qualitative ion M/z Qualitative ion 2 M/z Qualitative ion 3 M/z 1 picolinate 7.99 335.1 303.1 173.1 145.1 2 E-phenoxylate 8.17 238.1 191.1 167.1 284.1 3 ether bacteria Ester 8.37 206.1 131.1 116.1 313.2 4 Z-phenoxylate 8.45 196 191 238 345.9 5 pyrimidone ester 8.89 189.1 204.1 426.2 352.1 6 oxime strain 9.14 131.1 116.1 172.1 377.2 7 ether bacteria 9.88 295.2 16.1 237.2 not selected 8 oxime ether amide 10.23 205.2 132.1 221.1 116.1 9 pyrazole mushroom 11.41 325.0 132.0 164.0 not selected 10 fluoxibenolide 13.15 363.3 313.1 306.1 398.2 11 Azoxystrobin 14.90 344 372.1 388.1 403.2 7.3.3 Qualitative determination Under the above conditions, the reference retention time of 11 kinds of fungicides was about 7.9 min-15 min (see Table 1). standard Product Selection Ion Monitoring GC-MS Figure See Appendix A, Figure A.1. When the sample solution is measured according to the conditions determined by gas chromatography mass spectrometry, if the detected retention time of the chromatographic peaks is different from that in the standard solution And all selected ions are present in the sample mass spectrum after subtracting the background, and the selected ion abundance is proportional to the standard Of the ion abundance ratio within the allowable error range (see Table 2), you can determine the presence of such fungicides in Xiang products. If it can not be confirmed, should be heavy The new injection is further confirmed by means of scanning (if sufficient sensitivity) or by the addition of other confirmed ions. Table 2 The maximum allowable deviation of relative ion abundance when qualitative confirmation Relative abundance (base) 50% 20% to 50% 10% to 20% ≤10% Allowable relative deviation ± 20% ± 25% ± 30% ± 50% 7.3.4 Quantitative determination Quantitative determination using external standard method. According to the content of fungicides, select the peak area similar to the standard working solution together for chromatography Spectrum Analysis. The response values of the standard working solution and the fungicide in the sample to be measured should be within the linear range of the test. For standard working solutions and to be tested Sample volume and other volume into the plug sample. 7.4 blank experiment Unless the sample is not weighed, according to the above steps.

8 results are calculated and expressed

(1) to calculate the content of each fungicide in the sample by gas chromatography mass spectrometer workstation processing software, X = error did not find the reference source. (1) Where. X - the content of the fungicide in the sample in milligrams per kilogram, mg/kg; A - the chromatographic peak area of the fungicide in the sample solution; Ao - the peak area of the fungicide in the blank experiment; As - the chromatographic peak area of the fungicide in the standard solution; Cs - the concentration of the fungicide in the standard solution, in micrograms per milliliter, μg/mL; V - the final volume of the sample solution, in milliliters (mL); M - the amount of sample represented by the final sample, in grams, g. Note. The result of the calculation shall be deducted from the blank value. The result of the measurement shall be expressed as the arithmetic mean of the parallel measurement, and two valid digits shall be retained.

9 precision

9.1 The ratio of the absolute difference between the two independent determinations obtained under reproducibility and its arithmetic mean (percentage) shall be in accordance with Appendix D requirements. 9.2 The ratio of the absolute difference between the two independent determinations obtained under reproducibility and its arithmetic mean (percentage) shall be in accordance with Appendix E requirements. 10% limit and recovery rate 10.1 Quantitation limits In this method, the limit of the 11 fungicides in different matrices is given in Appendix B. 10.2 Recovery rate In this method, the recovery rates of 11 fungicides in various food matrices are given in Appendix C.

Appendix A

(Informative) Eleven methacrylic acid ester fungicides and GC-MS Table A.1 Molecular formula, molecular weight and American Chemical Abstracts for eleven methacrylic acid ester fungicides Serial number Pesticide Chinese name Pesticide English name CAS number Molecular formula Molecular weight retention time min Monitor the ion abundance ratio 1 azoxystrobin 131860-33-8 C22H17N13O5 403.12 14.90 344, 372.1, 388.1, 403.2

2 ether bacteria

Dimoxystrobi 141961-52-4 C19H22N2O3 326.16 9.88 295.2, 116.1, 237.2 3 pyrimethanone fluacrypyrim 229977-93-9 C20H21F3N2O5 426.14 8.89 189.1, 204.1, 426.2, 352.1 4 fluoxastrobin fluoxastrobin 361377-29-9 C21H16CIFN4 O5 458.08 13.15 363.3, 313.1, 306.1, 398.2

5 ether bacteria

Kresoxim-me Thyl 143390-89-0 C18H19NO4 313.13 8.37 206.1, 131.1, 116.1, 313.2 Z-phenoxy bacteria Z-metominos Trobin 133408-51-2 C16H16N2O3 284.12 8.45 196,191,238,345.9 E-phenoxy bacteria E-metominos Trobin 133408-50-1 C16H16N2O3 284.12 8.17 238.1, 191.1, 167.1, 284.1 8 oxime ether bacteria orysastrobin 248593-16-0 C18H25N5O5 405.2 10.23 205.2, 132.1, 221.1, 116.1

9 picolinate

Picoxystrobi 248593-16-0 C18H25N5O5 367.1 7.99 335.1, 303.1, 175.1, 145.1 Pyrazole bacteria Pyraclostrobi 175013-18-0 C19H18CIN3O 387.82 11.41 325.0, 182.0, 164.0 11 oxime ester Trifloxystrobi 142017-21-7 C20H19F3N2O4 408.13 9.14 131.1, 116.1, 172.1, 377.2 Note." "Marked ions are quantitative ions 1 - picolamate; 7 - 2 - E - phenoxamine; 8 - oxime; 3 - ether bacteria; 9-1 - pyrazole bacteria 1); 4 - Z - phenoxybenzamine; 10 - fluoxazole; 5 - pyrimidium ester; 9-2 - pyrazole bacteria; 6 - oxime; 11 - azoxystrobin Figure A.1 Eleven kinds of methacrylic acid ester fungicide standard gas chromatography-mass spectrometry total ion current 1) The GC-MS of the pyrazole bacteria showed bimodal (9-1, 9-2), the area of the two peaks under different concentration range and different chromatographic conditions The proportions are different. When the pyrazole bacteria is determined, the selective ion abundance ratio of the two peaks can be used as a qualitative basis, Under the conditions of the standard solution of the actual situation of the peak to choose a peak for the set. This standard selects the first peak during the experimental study For quantitative basis.

Appendix B

(Informative) The quantitative data of the sample is limited Table B.1 Experimental data on the quantitative limits of the sample Pesticide limit (mg/kg) Picolinate Bacteria E-phenoxy Fungi Ether bacteria Z-phenoxy Fungi Pyrimethanone oxime fungus ether ketone oxime ether bacteria Pyrazole Ether bacteria Fluorouracil Bacteria Azoxystrobin Apple 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.050 0.010 Grape 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Pear 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Cabbage 0.010 0.005 0.005 0.010 0.005 0.05 0.008 0.005 0.010 0.005 0.010 Cucumber 0.010 0.005 0.05 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Mushroom 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Orange juice 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 green tea Drink 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Chestnut 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Hair 0.010 0.005 0.005 0.010 0.005 0.005 0.008 0.005 0.010 0.005 0.010 Chicken 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Pork 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Beef 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Eggs 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Milk 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005

Appendix C

(Informative) Sample concentration and recovery of the experimental data Table C.1 Recovery range of eleven fungicides in fruit and vegetable substrates No. Pesticide Name Added Level/(mg/kg) Recovery rate/% Pear Mushroom Orange Juice Green Tea Drink Apple Grape Brassica

1 picolinate

0.01 87.56-104.17 72.70-94.70 80.39-87.01 82.69-109.77 73.15-101.85 78.31-111.62 80.46-109.08 80.92-112.15 0.02 79.14-97.68 72.50-96.35 79.79-98.48 88.38-98.23 72.35-98.12 76.15-101.96 73.00-94.27 72.69-94.38 0.06 71.87-100.88 86.77-104.29 70.96-99.62 83.26-99.05 82.31-104.28 74.65-102.28 76.25-100.06 78.65-95.97 E-phenoxy Fungi Lt;/RTI & gt; 88.53 Gt; 0.06 86.17-106.76 81.90-114.94 88.33-98.33 82.03-98.42 77.43-98.57 77.43-94.17 79.10-98.70 75.77-98.92

3 ether bacteria

0.01 83.44-108.73 81.02-96.84 88.62-96.35 81.23-111.92 78.69-99.38 78.69-107.08 81.08-111.69 80.77-104.23 0.02 87.21-97.65 88.81-101.66 88.12-98.66 81.69-99.42 91.96-101.23 81.23-101.62 79.85-100.96 80.92-103.27 0.06 88.83-102.75 78.57-104.52 87.89-101.66 83.83-103.12 78.49-96.54 78.49-92.88 79.88-102.55 79.88-102.08 Z-phenoxy Fungi Gt; 0.05 76.43-96.03 76.36-91.97 76.36-95.95 88.44-98.63 76.42-92.04 79.21-104.79 88.54-105.69 84.15-95.35 0.1 85.69-101.48 79.17-106.52 84.69-100.30 88.30-96.17 79.17-98.23 79.30-87.73 71.17-86.87 71.17-86.87

5 pyrimidium ester

0.01 93.50-108.14 84.56-106.47 84.56-116.47 80.10-118.40 85.60-106.20 76.20-95.60 80.70-113.60 82.70-115.60 0.02 89.14-100.20 88.50-105.40 91.85-103.25 80.30-98.40 85.35-104.80 77.25-93.85 77.45-96.20 72.20-96.00 0.05 95.85-102.10 81.23-112.43 96.60-102.90 88.08-103.98 81.22-98.02 81.22-98.02 83.98-99.02 80.08-99.98 Oxime ester 0.01 88.13-115.00 99.45-112.85 93.81-112.85 70.82-114.36 99.45-112.85 68.64-113.18 73.27-117.73 70.82-113.55 0.02 95.89-119.76 90.16-104.27 97.05-120.88 87.09-101.82 87.95-106.27 84.23-104.09 84.09-102.18 79.32-101.82 0.05 94.99-108.12 74.36-95.76 93.80-106.76 82.24-105.00 74.27-92.15 83.05-90.64 74.27-90.16 74.47-100.42

7 ether amine

0.02 91.12-115.60 81.20-102.08 81.20-102.08 83.88-109.24 81.41-102.00 84.24-99.06 83.53-110.82 83.88-109.24 0.09 95.99 0.08 94.33-102.12 85.21-105.47 94.00-101.76 83.12-100.76 90.76-105.52 85.28-95.08 86.35-97.44 83.94-98.14

8 oxime ether bacteria

0.01 91.22-101.44 80.20-97.36 80.20-97.36 72.50-111.60 80.40-97.60 70.20-91.50 77.20-117.00 77.50-110.70 0.02 96.03-103.21 86.05-95.65 90.10-97.00 80.80-97.65 76.80-95.50 76.80-95.70 73.50-99.20 72.85-97.65 0.05 91.22-106.87 73.95-99.46 90.90-106.50 84.42-97.08 73.52-99.56 77.86-96.82 75.68-97.81 77.08-96.82

9 pyrazole bacteria

0.02 90.17-105.70 91.40-108.40 91.40-103.20 82.14-110.50 81.48-99.22 81.48-17.08 83.52-111.00 83.40-110.10 0.05 90.09-96.98 86.20-105.14 84.40-103.98 83.37-96.02 80.35-102.30 80.35-98.35 86.29-98.08 77.77-98.23 0.08 10 fluoxazole ester 0.05 88.68-111.16 81.46-99.36 81.46-99.36 76.89-105.56 91.78-110.18 92.09-105.11 83.51-106.67 81.33-110.00 0.1 78.51-103.54 96.03-102.33 97.83-101.74 92.02-104.16 84.87-99.96...