• 분석과학
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• 제32권2호
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• pp.56-64
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• 2019

Recently, a number of adulterated products, which are advertised as hair-growth enhancer have been emerged among those who suffer hair loss disease. For continuous control of illegal products, in this study, a rapid and sensitive method for simultaneous screening of 12 compounds that enhance hair-growth was established to protect public health by ultrahigh-performance liquid chromatography coupled to quadrupole-orbitrap mass spectrometry (UHPLC-Q-Orbitrap-MS). Fragmentation pathways of them were proposed based on $MS^2$ spectral data obtained using the established method. In this analysis, the LODs and LOQs ranged from 0.05 to 50 ng/mL and from 0.17 to 167 ng/mL, respectively. The square of the linear correlation coefficient ($R^2$) was determined as more than 0.995. The intra- and inter-assay accuracies were respective 88-112 % and 88-115 %. Their precision values were measured within 5 % (intra-day) and 10 % (inter-day). Mean recoveries of target compounds in adulterated products ranged from 84 to 115%. The relative standard deviation of stability was less than 12 % at $4^{\circ}C$ for 48 h. The method was employed to screen 14 dietary supplements advertised to be effective for the treatment of hair loss. Some of the products (~21 %) were proven to contain synthetic drugs that promote hair growth such as triaminodil, minoxidil, and finasteride.

• 한국환경농학회지
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• 제39권4호
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• pp.368-374
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• 2020

BACKGROUND: The residual analysis of polar pesticides has remained a challenge. It is even more difficult to simultaneously analyze multiple polar pesticides. Diquat, paraquat, and chlormequat are typical examples of highly polar pesticides. The existing methods for the analysis of diquat, paraquat and chlormequat are complex and time consuming. Therefore, a simple, quick and effective method was developed in the represent study for simultaneous analysis of diquat, paraquat and chlormequat in animal products, meat and fat using UPLC-MS/MS. METHODS AND RESULTS: Sample extraction was carried out using acidified acetonitrile and water and re- extracted with acidified acetonitrile and combine the extracts followed by centrifugation. The extract was then cleaned up with a HLB cartridge after reconstitution with acidic acetonitrile and water. The method was validated in quintuplicate at three different concentrations. The limits of detection (LOD) and quantification (LOQ) were 0.0015 and 0.005 mg/L, respectively. Matrix suppression effect was observed for all of the analytes. A seven point matrix matched calibration curve was constructed for each of the compound resulted excellent linearity with determination coefficients (R2) ≥ 0.991. Accuracy and precision of the method was calculated from the recovery and repeatability and ranged from 62.4 to 119.7% with relative standard deviation less than 18.8%. CONCLUSION: The recovery and repeatability of the developed method were in the acceptable range according to the Codex Alimentarius guideline. The developed method can be applied for the routine monitoring of diquat, paraquat, and chlormequat in animal products, meat and fat.

• 한국동물위생학회지
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• 제43권4호
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• pp.261-265
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• 2020

Each commercial cyromazine insecticide has different HPLC conditions. The aim of this study was to establish a standardized chromatographic method for the determination of cyromazine in commercial insecticides. The separation was achieved on two C18 columns - Waters® Bondapak C (4×300 nm i.d., 10 ㎛) and X bridge (4.6×250 nm i.d., 5 ㎛) using a mobile phase composed of water/methanol/ethanolamine (76:24:0.1, v/v), with UV detection at wavelengths 230 nm and 254 nm. A total of six commercial cyromazine insecticides were analyzed. In this study, the optimal high-performance liquid chromatography conditions for the analysis of cyromazine were as follows: a mobile phase of water/methanol/ethanolamine (76:24:0.1, v/v) at a flow rate of 1.0 mL/min and a detection wavelength of 230 nm using a X bridge C18 column (4.6×250 nm i.d., 5 ㎛) at a column temperature of 25℃. The calibration curve was linear in the concentration range of 5~50 ㎍/mL, with a correlation coefficient of 0.99995. The cyromazine detection limit was 0.2 ㎍/mL, and the limit of quantification was 0.59 ㎍/mL. The percentage recovery ranged from 99.8% to 101.0% for cyromazine, and the relative standard deviation was not over 2.0%. The cyromazine concentration ranged from 92.7% to 109.4% and was within the acceptable range (90~120%) for the percent of the labeled amount. This method was found to be suitable for determining cyromazine in commercial insecticides.

• 생약학회지
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• 제51권4호
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• pp.270-277
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• 2020

This study analyzed mycotoxins, aflatoxin B1, B2, G1, G2, fumonisin B1, B2, ochratoxin A and zearalenone, using LC-MS/MS and conducted risk assessment on 54 samples of seeds distributed in SeoulYangnyeongsi and the management status of extramural herbal dispensary facility. The matched calibration showed a good linearity as observed in 6 concentration levels(r2>0.999) as a result of method validation applied with Arecae semen. Limits of detection(LOD) and quantification(LOQ) were in the range of 0.02-0.11 ㎍/kg and 0.08-0.34 ㎍/kg, respectively. Recoveries also estimated, ranging from 65.1-99.7% with relative standard deviation(RSD) 0.5-6.3%. As a result of the method on 54 samples, mycotoxins were detected in 16 samples. Among them, two Thujae semen showed a degree of concentration that exceeded the aflatoxin specification. In the risk assessment, the human exposure safety standard values were calculated as ADI(Acceptable Daily Intake) for aflatoxin B1, fumonisin and zearalenone. Ochratoxin A was calculated as PTWI(Provisional Tolerable Weekly Intake). The MOE(Margine of Exposure) of aflatoxin B1 was in the range of 40.36-3536.88. And no items exceeded 100% in %TDI(Tolerable Daily Intake) and %TWI(Tolerable Weekly Intake) of fumonisin, zearalenone and ochratoxin A.

• The Plant Pathology Journal
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• 제37권2호
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• pp.173-181
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• 2021

The genus Streptomyces demonstrates enormous promise in promoting plant growth and protecting plants against various pathogens. Single and consortium treatments of two selected Streptomyces strains (Streptomyces shenzhenensis TKSC3 and Streptomyces sp. SS8) were evaluated for their growth-promoting potential on rice, and biocontrol efficiency through induced systemic resistance (ISR) mediation against Xanthomonas oryzae pv. oryzicola (Xoc), the causal agent of rice bacterial leaf streak (BLS) disease. Seed bacterization by Streptomyces strains improved seed germination and vigor, relative to the untreated seed. Under greenhouse conditions, seed bacterization with consortium treatment TKSC3 + SS8 increased seed germination, root length, and dry weight by 20%, 23%, and 33%, respectively. Single and consortium Streptomyces treatments also successfully suppressed Xoc infection. The result was consistent with defense-related enzyme quantification wherein single and consortium Streptomyces treatments increased peroxidase (POX), polyphenol oxidase, phenylalanine ammonia-lyase, and β,1-3 glucanase (GLU) accumulation compared to untreated plant. Within all Streptomyces treatments, consortium treatment TKSC3 + SS8 showed the highest disease suppression efficiency (81.02%) and the lowest area under the disease progress curve value (95.79), making it the best to control BLS disease. Consortium treatment TKSC3 + SS8 induced the highest POX and GLU enzyme activities at 114.32 µmol/min/mg protein and 260.32 abs/min/mg protein, respectively, with both enzymes responsible for plant cell wall reinforcement and resistant interaction. Our results revealed that in addition to promoting plant growth, these Streptomyces strains also mediated ISR in rice plants, thereby, ensuring protection from BLS disease.

• 한국축산식품학회지
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• 제41권1호
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• pp.59-70
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• 2021

A method for simultaneous detection of fipronil (F) and its metabolites fipronil desulfinyl (FD), fipronil sulfide (FS), fipronil sulfone (FSO) in chicken eggs was applied and validated. It includes single-step, cheap, effective, rugged, safe-based method (SinChERS) for sample preparation and ultra high performance liquid chromatography coupled with mass spectrometry (UHPLC-MS/MS) for chemical analysis. Results suggested that formic acid enhanced the recovery of 4 target residues and 1% supplementation to acetonitrile gained higher recoveries than that of 5%. SinChERS integrated extraction and clean-up steps into one, with shorter time (1.5 h) to operate and higher recoveries (97%-100%) than HLB, Envi-Carb-NH2 and quik-easy-cheap-effective-rugged-safe method (QuEChERS), and it consumed the smallest volume of extracting solvent (10 mL) as QuEChERS. Quantitative analyses using external standard method suggested the linear ranges of 4 target compounds were 1-20 ㎍/L with R2 >0.9947. The limit of detection (S/N>3) and quantification (S/N>10) were 0.3 ㎍/kg and 1 ㎍/kg. Recoveries ranged from 89.0% to 104.4%, and the relative standard deviations (n=6) at 1, 10, and 20 ㎍/kg were lower than 6.03%. Thirty batches of domestic eggs (500 g each) were detected by the established SinChERS-based UHPLC-MS/MS and no target residues were detected in all samples. The method developed in this study is a rapid, sensitive, accurate and economic way for multi-residue analysis of fipronil and its metabolites in eggs.

• Journal of Veterinary Science
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• 제23권4호
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• pp.56.1-56.17
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• 2022

Background: At the therapeutic doses, diclofenac sodium (DFS) has few toxic side effects on mammals. On the other hand, DFS exhibits potent toxicity against birds and the mechanisms remain ambiguous. Objectives: This paper was designed to probe the toxicity of DFS exposure on the hepatic proteome of broiler chickens. Methods: Twenty 30-day-old broiler chickens were randomized evenly into two groups (n = 10). DFS was administered orally at 10mg/kg body weight in group A, while the chickens in group B were perfused with saline as a control. Histopathological observations, serum biochemical examinations, and quantitative real-time polymerase chain reaction were performed to assess the liver injury induced by DFS. Proteomics analysis of the liver samples was conducted using isobaric tags for relative and absolute quantification (iTRAQ) technology. Results: Ultimately, 201 differentially expressed proteins (DEPs) were obtained, of which 47 were up regulated, and 154 were down regulated. The Gene Ontology classification and Kyoto Encyclopedia of Genes and Genomes pathway analysis were conducted to screen target DEPs associated with DFS hepatotoxicity. The regulatory relationships between DEPs and signaling pathways were embodied via a protein-protein interaction network. The results showed that the DEPs enriched in multiple pathways, which might be related to the hepatotoxicity of DFS, were "protein processing in endoplasmic reticulum," "retinol metabolism," and "glycine, serine, and threonine metabolism." Conclusions: The hepatotoxicity of DFS on broiler chickens might be achieved by inducing the apoptosis of hepatocytes and affecting the metabolism of retinol and purine. The present study could provide molecular insights into the hepatotoxicity of DFS on broiler chickens.

• Mass Spectrometry Letters
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• 제13권3호
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• pp.58-83
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• 2022

We developed analytical methods using high performance chromatography (HPLC) and liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 80 unapproved compounds in dietary supplements. The target compounds for analysis were unapproved ingredients (e.g., pharmaceuticals) that have potential adverse effects on consumers owing to accidental misuse, overuse, and interaction with other medication in dietary supplement. Two analytical methods were tested to identify the optimal validation results according to AOAC guideline. As a result, limit of quantification (LOQ) was 0.14-0.5 ㎍ mL^-1; linearity (r²) was ≥ 0.99; accuracy (expressed as recovery) was 78.9-114%; precision (relative standard deviation) was ≤ 4.28% in the HPLC method. In the LC-MS/MS method, LOQ was 0.01-2 ng mL^-1, linearity (r²) was ≥0.98, accuracy was 71.7-119%; precision was ≤ 12.5%. The developed methods were applied to 51 dietary supplements collected from 2019 to 2021 through MFDS alert system. Based on our previous monitoring study, major compounds were icariin, sibutramine, yohimbine, sildenafil, tadalafil, sennosides (A, B), cascarosides (A, B, C, D), and phenolphthalein. In this study, we re-analyzed samples of detected compounds, and evaluated the statistical difference using Bland-Altman analysis to compare two analytical approaches between HPLC and LC-MS/MS. These results showed a good agreement between two methods that can be used to monitor the unapproved ingredients in dietary supplements. The developed two methods are complementarily suitable for monitoring the adulteration of 80 unapproved compounds in dietary supplements.

• Natural Product Sciences
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• 제28권4호
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• pp.187-193
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• 2022

Lysimachia christinae Hance was commonly used in Oriental medicine for treating the hepatitis virus, cholecystitis and cholagogic efficiency. According to the previous study, it possesses high antioxidant and anti-inflammatory activity. Simultaneous determination analytical method of isolated eight compounds, cynaroside (1), 2-(3,4-dimethoxyphenyl) ethyl O-α-L-arabinopyranosyl-(1→2)-O-[6-deoxy-α-L-mannopyranosyl-(1→3)] β-D-glucopyranoside (2), stearylester ricinoleic acid (3), (E)-4-(3,4-dimethoxyphenyl) but-3-en-1-yl palmitate (4), 2-hydroxy-24-methoxy-4-tetracosenoic acid (5), 2-hydroxy-24-propoxy-4-tetracosenoic acid (6), β-sitosterol (7), and androst-16-ene-3,6-diol (8) were established by using HPLC-DAD. This HPLC analysis was detected on a Dionex C18 column (5 ㎛, 120 Å, 4.6 mm × 150 mm) at 25℃. The mobile phase consisted of 0.1% trifluoroacetic acid and acetonitrile at a flow rate of 1 mL/min. Validation of the method was assessed by linearity, precision and accuracy test. Calibration curve was good at r² > 0.9998. Limits of detection (LOD) ranged from 0.19 to 8.18 g/ml and Limits of quantification (LOQ) ranged from 0.19 to 24.80 g/ml. The relative standard deviations (RSD) values of precision test, intra- and inter- day, were less than 0.99% and 1.0%. The accuracy test results ranged from 98.81% to 106.49% and RSD values were less than 0.95%. These results showed that the HPLC-DAD method was very reliable and accurate for the quantity analysis of eight compounds in L. christinae extract for quality control.

• 한국환경농학회지
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• 제42권2호
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• pp.93-103
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• 2023

Persistence and degradation patterns of acequinocyl and its metabolite, hydroxyl-acequinocyl (acequinocyl-OH) and fenpyroximate in butterburs (Petasites japonicus Max.) were investigated after pesticide application. Butterburs, one of the minor crops in South Korea, was planted in two plots (plot A for double and plot B for single application) in a greenhouse. Butterburs samples were also planted in a separate plot without pesticide treatment, as the control. A commercial pesticide containing acequinocyl and fenpyroximate was applied to the foliage of butterburs at hourly intervals after dilution. Recoveries of acequinocyl and acequinocyl-OH were 78.6-84.7% and 83.7-95.5%, respectively; the relative standard deviation of the two compounds were less than 5%. The method limit of quantification was 0.01 mg/kg. The total (Ʃ) acequinocyl residues in butterburs reduced by 96.0% at 14 days and 75.9% at 7 days, in plot A and B, respectively, after final pesticide applications. The biological half-life (DT₅₀) of Ʃ acequinocyl and fenpyroximate, calculated using the dissipation rate, was 3.0 days and 4.0 days, respectively. These data were used to set up maximum residue and safe standard levels when the pesticides are applied to control pests during butterbur cultivation. Risk assessment results showed that the maximum % acceptable daily intake was 7.74% for Ʃ acequinocyl and 0.16% for Ʃ fenpyroximate. The theoretical maximum daily intake of Ʃ acequinocyl and fenpyroximate was 26.3% and 35.8%, respectively. In conclusion, the concentrations of Ʃ acequinocyl and fenpyroximate in butterburs pose no significant health risks to Koreans.