• The Korean Journal of Pesticide Science
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• v.21 no.1
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• pp.68-74
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• 2017

An analytical method for detecting metamifop residue in paddy water, soil, and rice with high performance liquid chromatography (HPLC) was developed. Water was extracted with ethyl acetate before analyzing by HPLC. Soil residues were extracted with acetone under acidic condition and after purifying with $Extrelut^{(R)}$ NT, and silica SPE, the residue was analyzed by HPLC. For residue analysis in rice, the procedure involved extraction with acetone, purification with $Extrelut^{(R)}$ NT, partitioning between acetonitrile/hexane, purification with silica SPE cartridge, and analysis by HPLC. The limit of detection (LOD) was 1.0 ng, limit of quantitation (LOQ) was 3.0 ng, and method limit of quantitation (MLOQ) were 0.001 mg/L for paddy water, 0.01 mg/kg for rice and soil, respectively. Standard calibration curve shows linearity from 0.05 mg/kg to 5.0 mg/kg ($R^2=0.9999$). The recoveries in fortified paddy water were $91.3{\pm}3.5%$ (0.01 mg/L level) and $93.2{\pm}6.3%$ (0.05 mg/L level). The recoveries in fortified paddy soils were $92.5{\pm}4.0%$ (0.1 mg/kg level) and $92.7{\pm}4.0%$ (0.5 mg/kg level) in soil A, while, $102.3{\pm}4.4%$ (0.1 mg/kg level) and $98.9{\pm}7.9%$ (0.5 mg/kg level) in soil B, respectively. The recoveries in fortified rice were $93.0{\pm}6.9%$ (0.1 mg/kg level) and $85.0{\pm}3.5%$ (0.5 mg/kg level). This method was proved to be effective and can be used to determine the metamifop residue in paddy water, paddy soil, and rice.

• Korean Journal of Food Science and Technology
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• v.45 no.6
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• pp.693-699
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• 2013

A simple, sensitive, and specific method for quantifying the nicotine content of synthetic favoring substances (SFS) was developed using high performance liquid chromatography (HPLC) with a photo-diode array detector (PDA). Nicotine was extracted from SFS samples by using an acid-base liquid-liquid extraction method with dichloromethane and distilled water. The nicotine content was quantified by HPLC/PDA (261.9 nm) with a $C_{18}$ column under a gradient of 10% acetonitrile with 20 mM ammonium formate (ammonia solution adjusted to pH 8.7) to 100% acetonitrile. The calibration curve, analyzed from concentration standards between 0.1 to 2 mg/L, presented linearity with a correlation coefficient ($r^2$)>0.9999. The limit of quantitation (LOQ) of nicotine in SFS was 0.4 mg/kg, and the average recoveries ranged from 76.4% to 96.3%. The repeatability of measurements, expressed as the coefficient of variation (CV%), ranged from 1.74 to 5.12%. This newly developed method for nicotine quantification in SFS can be considered an analytical method with an acceptable level of sensitivity and repeatability.

• Journal of Food Hygiene and Safety
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• v.26 no.2
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• pp.142-149
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• 2011

An isocratic high performance liquid chromatography (HPLC) method for routine analysis of deoxynivalenol in noodles was validated and estimated the measurement uncertainty. Noodles (dried noodle and ramyeon) were analyzed by HPLC-ultraviolet detection using immunoaffinity column for clean-up. The limits of detection (LOD) and quantification (LOQ) were 7.5 ${\mu}g$/kg and 18.8 ${\mu}g$/kg, respectively. The calibration curve showed a good linearity, with correlation coefficients $r^2$ of 0.9999 in the concentration range from 20 to 500 ${\mu}g$/kg. Recoveries and Repeatabilities expressed as coefficients of variation (CV) spiked with 200 and 500 ${\mu}g$/kg were $82{\pm}2.7%$ and $87{\pm}1.3%$% in dried noodle, and $97{\pm}1.6%$ and $91{\pm}12.0%$ in ramyeon, respectively. The uncertainty sources in measurement process were identified as sample weight, final volume, and sample concentration in extraction volume as well as components such as standard stock solution, working standard solution, 5 standard solutions, calibration curve, matrix, and instrument. Deoxynivalenol concentration and expanded uncertainty in two matrixes spiked with 200 ${\mu}g$/kg and 500 ${\mu}g$/kg were estimated to be $163.8{\pm}52.1$ and $435.2{\pm}91.6\;{\mu}g$/kg for dried noodle, and $194.3{\pm}33.0$ and $453.2{\pm}91.1\;{\mu}g$/kg for ramyeon using a coverage factor of two which gives a level of statistical confidence with approximately 95%. The most influential component among uncertainty sources was the recovery of matrix, followed by calibration curve.

• Analytical Science and Technology
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• v.25 no.1
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• pp.76-82
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• 2012

The determination and confirmation of dutasteride in human serum was performed by a liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS). Beclomethasone as an internal standard (I.S.) was added to the serum and the mixed sample was pretreated by liquid-liquid extraction (LLE) with methyl tert-butyl ether (MTBE). The mass transitions of dutasteride and I.S. monitored in multiple reaction monitoring (MRM) were m/z 529.6${\rightarrow}$461.5 and m/z 409.3${\rightarrow}$391.2, respectively, and the retention times were 6.45 and 5.46 min, respectively. The calibration curve was linear in the concentration range of 0.5~30.0 ng/mL ($R^2$= 0.9999) and the limit of quantitation (LOQ) was found to be 0.5 ng/mL. The recovery of dutasteride was shown to be 66~72%. The intra-day assay precision and accuracy were in the range 3.5~5.5% and 85.7~89.9%, respectively, and the interday assay precision and accuracy were in the range 4.2~5.8% and 90.8~95.8%, respectively.

• The Korean Journal of Pesticide Science
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• v.16 no.4
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• pp.273-281
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• 2012

This study was conducted for the establishment of the analytical method of pesticide residues in rice straw for 9 pesticides; etofenprox, tricyclazole, diazinon, edifenphos, propiconazole, carbaryl, carbofuran, 3-hydroxy carbofuran and 3-keto carbofuran and for the monitoring of these pesticides in rice straw for livestock feed in Korea. These pesticides were classified into 4 groups according to analytical instrument condition. Group 1 (HPLC-UVD1) included tricyclazole and etofenprox while group 2 (HPLC-UVD2) included propiconazole and edifenphos. Group 3 (HPLC-FLD) included carbaryl, carbofuran, 3-hydroxy carbofuran and 3-keto carbofuran. Group 4 (GC-NPD) included Diazinon. The dried rice straw samples were extracted with acetone and purified by liquid-liquid partition and solid phase extraction (SPE): Combination of Florisil SPE and amino-propyl SPE was used for group 1 and group 2, amino-propyl SPE for group 3, and Florisil SPE was for group 4. Recovery was in the ranged 70~110% and the limits of quantitation (LOQ) were lower than the half of maximum residue limits. Therefore this method was proved to be efficient for monitoring of these pesticides residue in rice straw. A total of 18 rice straw samples from 6 provinces in Korea in 2010 were analyzed using established method and, only 3-keto carbofuran was detected in one sample at concentration of 0.04 mg/kg.

• The Korean Journal of Pesticide Science
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• v.15 no.3
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• pp.254-268
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• 2011

Fenoxycarb, pyriproxyfen and methoprene are juvenile hormone mimic insecticide. These insecticides have been widely used for mosquito, fly, scale insects, and Lepidoptera. The purpose of this study was to develop a simultaneous determination procedure of fenoxycarb, pyriproxyfen and methoprene residues in crops using HPLC-UVD/MS. These insecticide residues were extracted with acetone from representative samples of four raw products which comprised brown rice, apple, green pepper, and Chinese cabbage. The extract was diluted with saline water, and then n-hexane/dichloromethane partition was followed to recover these insecticides from the aqueous phase. Florisil column chromatography was additionally employed for final clean up of the extract. The analytes were quantitated by HPLC-UVD/MS, using a $C_{18}$ column. The crops were fortified with each insecticide at 3 levels per crop. Mean recovery ratios were ranged from 80.0 to 104.3% in four representative agricultural commodities. The coefficients of variation were less than 4.8%. Quantitative limit of fenoxycarb, pyriproxyfen, and methoprene was 0.04 mg/kg in crop samples. A HPLC-UVD/MS with selected-ion monitoring was also provided to confirm the suspected residues. The proposed simultaneous analysis method was reproducible and sensitive enough to determine the residues of fenoxycarb, pyriproxyfen and methoprene in the agricultural commodities.

• Korean Journal of Food Science and Technology
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• v.39 no.4
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• pp.372-379
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• 2007

A high-performance liquid chromatography-electrospray ionization (HPLC-ESI) tandem MS was developed for the rapid and simultaneous determination of forbidden medicines in dietary supplements. Thirteen medicinal components such as PDE-5 inhibitors and their analogues, and the newly identified dimethylsildenafil and xanthoanthrafil, were included in this study. After tentative standardization of molecular ions in both polarities using thirteen references on the mass spectrometer, with ESI-continuous infusion via the syringe pump method, the relative intensity of the ions present in the resulting spectra was quantitatively compared. From the results, the ion mode was selected depending on each reference's characteristics. A HPLC method coupled with the ESI mode was developed considering the matrix effect and interference depending on the type of sample. The validation test of the developed method was followed by carrying out precision, accuracy, recovery, sensitivity and linearity, etc. The method showed sufficiently high sensitivity, reproducibility, and specificity, and produced 4 times faster results when compared with the existing HPLC/UV method for the determination of forbidden compounds in dietary supplements.

• Korean Journal of Environmental Agriculture
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• v.31 no.2
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• pp.157-163
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• 2012

BACKGROUND: For the safety of imported agricultural products, the study was conducted to develop the analytical method of unregistered pesticides in domestic. The analytical method of 6 pesticides, chlorthal-dimethyl, clomeprop, diflufenican, hexachlorobenzene, picolinafen, and propyzamide, for a fast multi-residue analysis were established for two different type crops, orange and brown rice by GC-ECD and confirmed by mass spectrometry. METHODS AND RESULTS: The analytical method was evaluated to limit of quantification, linearity and recoveries. The crop samples were extracted with acetonitrile and performed cleanup by liquid-liquid partition and Florisil SPE to remove co-extracted matrix. The extracted samples were analyzed by GC-ECD with good sensitivity and selectivity of the method. The limits of quantification (LOQ) range of the method with S/N ratio of 10 was 0.02~0.05 mg/kg for orange and brown rice. The linearity for targeted pesticides were $R^2$ >0.999 at the levels ranged from 0.05 to 10.0 mg/kg. The average recoveries ranged from 74.4% to 110.3% with the percentage of coefficient variation in the range 0.2~8.8% at two different spiking levels (0.02 mg/kg and 0.2 mg/kg, 0.05 mg/kg and 0.5 mg/kg) in brown rice. And the average recoveries ranged from 77.8% to 118.4% with the percentage of coefficient variation in the range 0.2~6.6% at two different spiking levels (0.02 mg/kg and 0.2 mg/kg, 0.05 mg/kg and 0.5 mg/kg) in orange. Final determination was by gas chromatography/mass spectrometry/selected ion monitoring (GC/MS/SIM) to identify the targeted pesticides. CONCLUSION: As a result, this developed analytical method can be used as an official method for imported agricultural products.

• Journal of Food Hygiene and Safety
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• v.32 no.5
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• pp.381-388
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• 2017

In this study, we investigated the levels of natural preservatives of benzoic acid, sorbic acid, and propionic acid in spices. The quantitative analysis was performed using high performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) for benzoic acid and sorbic acid and gas chromatography-mass spectrometry (GC-MS) for propionic acid. The sample was extracted with ethanol using sonication, then centrifuged and evaporated to dryness and redissolved to 1 mL with ethanol to use for the instrumental analysis. The analytical method was validated based on linearity, recovery, limit of detection (LOD), and limit of quantification (LOQ). This method was suitable to determine low amounts of naturally occurring preservatives (benzoic acid, sorbic acid, and propionic acid) in various spices. Benzoic acid, sorbic acid, and propionic acid were found in 165 samples, 88 samples, and 398 samples, respectively from the total of 493 samples. The concentration of benzoic acid, sorbic acid, and propionic acid were ranged at ND-391.99 mg/L, ND-57.70 mg/L, and ND-188.21 mg/L in spices, respectively. The highest mean levels of benzoic acid, sorbic acid, and propionic acid were found in cinnamon (167.15 mg/L), basil leaves (22.79 mg/L), and white pepper (51.48 mg/L), respectively. The results in this study provide ranges of concentration regarding naturally occurring benzoic acid, sorbic acid, and propionic acid in spices. Moreover, the results may use to the case of consumer complaint or trade friction due to the inspection services of standard criteria for the preservatives of spices.

• Journal of Food Hygiene and Safety
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• v.32 no.4
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• pp.298-305
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• 2017

Benzovindiflupyr is a new pyrazole carboxamide fungicide that inhibits succinate dehydrogenase of mitochondrial respiratory chain. This study was carried out to develop an analytical method for the determination of benzovindiflupyr residues in agricultural commodities using LC-MS/MS. The benzovindiflupyr residues in samples were extracted by using acetonitrile, partitioned with dichloromethane, and then purified with silica solid phase extraction (SPE) cartridge. Correlation coefficient ($r^2$) of benzovindiflupyr standard solution was 0.99 over the calibration ranges ($0.001{\sim}0.5{\mu}g/mL$). Recovery tests were conducted on 5 representative agricultural commodities (mandarin, green pepper, potato, soybean, and hulled rice) to validate the analytical method. The recoveries ranged from 79.3% to 110.0% and then relative standard deviation (RSD) was less than 9.1%. Also the limit of detection (LOD) and limit of quantification (LOQ) were 0.0005 and 0.005 mg/kg, respectively. The recoveries of interlaboratory validation ranged from 83.4% to 117.3% and the coefficient of variation (CV) was 9.0%. All results were followed with Codex guideline (CAC/GL 40) and Ministry of Food and Safety guideline (MFDS, 2016). The proposed new analytical method proved to be accurate, effective, and sensitive for benzovindiflupyr determination and would be used as an official analytical method.