• Analytical Science and Technology
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• v.6 no.1
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• pp.9-19
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• 1993

Fatty acid salts derived from soap can be transferred into a typical derivative with p-bromophenacyl bromide using crown ether, a catalizer by the solid-liquid phase transfer reaction in nonpolar, aprotic solvents and separated by the reverse phase high performance liquid Chromatography (RP-HPLC) and determined using UV detector. The minimal limit of detection was defined at approximately 10~50ng in accordance with the chain length. The derivatization reaction in the presence of EDTA can be applied mot only to the calcium salts but also to the other various metal salts. The recoveries of fatty acid derivatizations in the absence and presence of the midium containing the yeast extract were obtained $95.4{\pm}1.2$, and $85.2{\pm}2.4%$ respectively. The analytical method would be applicable to determine the biodegradation of fatty acid salts in nature as well as in artificial condition such as shaker flask-medium method.

• Analytical Science and Technology
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• v.22 no.5
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• pp.407-414
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• 2009

A simultaneous determination method for cholesterol, lanosterol and desmosterol was developed using gas chromatography/mass spectrometry. Urine was enzymatically hydrolyzed with ${\beta}$-glucuronidase/arylsulfatase. Samples were prepared using extractions with a mixture of ethyl acetate-hexane (2:3, v/v), followed by derivatization with a mixture of MSTFA/TMSI/TMCS (100:2:5 v/v/v). All analyses were performed using GC/MS in selective ion monitoring mode. Good linearities ($r^2=0.998{\sim}0.999$) in calibration curve and a satisfactory recovery (80.0%~113%) were achieved. Accuracy and precision values within ${\pm}15%$ in the concentration range of 5 to 200 ng/mL were also observed for all compounds. The developed method was applied to pravastatin-treated (70 and 250 mg/kg/day for 7 days, oral) hyperlipidemia rats. Those sterols were significantly lower in drug-treated rats compared to the controls, which justifies the drug efficacy. Therefore, these results indicate that the developed method was successfully applied to examine statin drug efficacy with urine sample.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.9 no.1
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• pp.23-40
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• 1999

The analysis of thiodiglycolic acid in urine has been used as an index of biological exposure to vinyl chloride. Unfortunately thiodiglycolic acid has a strong hydrophilic character, because it has two carboxylic groups, so that it can only be extracted with organic solvent with a great difficulty. Underivatized thiodiglycolic acid tends to tail because of non-specific interaction with the inert support. Therefore, esterification is the obvious first choice for derivatization of thiodiglycolic acid, particularly for gas chromatography. In this study, the focus of interest is to compare two method of esterifications (methylation and silylation). Methylation is to make the methyl ester of thiodiglycolic acid by reaction with diazomethane. Silylation is to make the trimethylsilyl ester of thiodiglycolic acid by reaction with N-trimethylsily-ldiethylamine. The results and conclusions are as the following: 1. The detection limit (sensitivity) of methylated thiodiglycolic acid was $5.00{\mu}g/m{\ell}$ and silylated thiodiglycolic acid was $3.07{\mu}g/m{\ell}$ by gas chromatography with flame ionization detector. 2. The optimal liquid-liquid extraction of thiodiglycolic acid was as following: To each of the tubes, $15m{\ell}$ of urine, concentrated sulfuric acid (pH 1 - 2) and 5 gsodium sulfate were added. The samples was extracted three times with $5m{\ell}$ ethylacetate each time. 3. The methylated thiodiglycolic acid was more stable than silylated thiodiglycolic acid in extractional solvent which contained humidity. 4. The precision (pooled coefficient of variation for 4 days) of the analysis was 0.07324 in methylated thiodiglycolic acid with external standard calibration, and 0.07033 in methylated thiodiglycolic acid with internal standard calibration. 5. The precision (pooled coefficient of variation for 4 days) of the analysis was 0.10914 in silylated thiodiglycolic acid with external standard calibration, and 0.13602 in silylated thiodiglycolic acid with internal standard calibration. From the above results, the analysis of methylated thiodiglycolic acid was more sensitive (limit of detection) than silylated thiodiglycolic acid by gas chromatography. However, the methylated thiodiglycolic acid was stable in the humidity and was separated sharply on chromatogram. Also, analysis of methylated thiodiglycolic acid was more precise (pooled coefficient of variation for 4 days) than silylated thiodiglycolic acid. In conclusion, it is established that the analysis of methylated thiodiglycolic acid is appropriate for biological monitoring of exposure to vinyl chloride.

• Korean Journal of Environmental Agriculture
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• v.36 no.1
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• pp.63-66
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• 2017

BACKGROUND: The phenol concentrations in water samples were determined using gas chromatography after derivatization of the analyte to phenyl acetate followed by extraction using a large volume of solvent. However, this procedure requires an additional purification step and is not analytically efficient. METHODS AND RESULTS: In this study, phenol was first extracted from an acidified water sample using ethyl acetate and then acetylated using acetic anhydride in the presence of a small amount of water and $K_2CO_3$. The derivative was extracted using 1mL of n-butyl acetate. One microliter of the extract was analyzed by GC-MS without further purification. The calibration curve showed good linearity with the $r^2$ value of 0.9968. The method detection limit and the limit of quantitation were estimated to be $0.18{\mu}g/L$ and $0.56{\mu}g/L$, respectively. Repeatability (RSD, n=3) and recovery (n=3) were 9.1%-4.3% and 90.6%-110.5%, respectively. The concentrations of phenol in a few samples of stream water were distributed in the range of $2.51-7.51{\mu}g/L$. CONCLUSION: This method is simpler and faster to implement than those currently utilized and shows high analytical reliability. It can be applied to the quantitative determination of phenol concentrations in surface water and groundwater samples.

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.559-565
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• 2003

An analytical method the determination of benzo(a)pyrene (BaP) and its hydroxylated metabolites, 1-hydroxybenzo(a)pyrene (1-OHBaP), 3-hydroxybenzo(a)pyrene (3-OHBaP), benzo(a)pyrene-4,5-dihydrodiol (4,5-diolBaP) and benzo(a)pyrene-7,8-dihydrodiol (7,8-diolBaP), in rat urine and plasma has been developed by HPLC/FLD and GC/MS. The derivatization with alkyl iodide was employed to improve the resolution and the detection of two mono hydroxylated metabolites, 1-OHBaP and 3-OHBaP, in LC and GC. BaP and its four metabolites in spiked urine were successfully separated by gradient elution on reverse phase ODS $C_{18}$ column (4.6 mm I.D., 100 mm length, particle size 5 ㎛) using a binary mixture of MeOH/H₂O (85/15, v/v) as mobile phase after ethylation at 90 ℃ for 10 min. The extraction recoveries of BaP and its metabolites in spiked samples with liquid-liquid extraction, which was better than solid phase extraction, were in the range of 90.3- 101.6% in n-hexane for urine and 95.7-106.3% in acetone for plasma, respectively. The calibration curves has shown good linearity with the correlation coefficients (R²) varying from 0.992 to 1.000 for urine and from 0.996 to 1.000 for plasma, respectively. The detection limits of all analytes were obtained in the range of 0.01-0.1 ng/mL for urine and 0.1-0.4 ng/mL for plasma, respectively. The metabolites of BaP were excreted as mono hydroxy and dihydrodiol forms after intraperitoneal injection of 20 mg/kg of BaP to rats. The total amounts of BaP and four metabolites excreted in dosed rat urine were 3.79 ng over the 0-96 hr period from adminstration and the excretional recovery was less than 0.065% of the injection amounts of BaP. The proposed method was successfully applied to the determination of BaP and its hydroxylated metabolites in rat urine and plasma for the pharmacokinetic studies.

• Journal of Environmental Health Sciences
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• v.36 no.1
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• pp.52-60
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• 2010

High performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS) have been widely used to quantify aflatoxins in food, but these methods are expensive, time-consuming, unsuitable for analysis of the routine screening of large sample numbers and require derivatization and high level techniques to perform. The objective of this study is to detect aflatoxins in a large number of foods by a high efficient analytical system of combined enzyme linked immunosorbent assay (ELISA) for screening and LC/MS/MS for confirmation. The samples spiked individually with aflatoxin $B_1$ (0.5 and 1.0 ng/g) and total aflatoxins (10 ng/g) were analyzed by ELISA and LC/MS/ MS, and the recoveries for ELISA and LC/MS/MS were 71.8~119.2% and 70.8~135.3%, respectively. A total of 378 samples (grains, nuts, soybean and fermented soybean foods, pepper and fermented pepper foods) were purchased from the six major cities in Korea and analyzed by ELISA-LC/MS/MS system. Twenty two (5.8%; peanut: 11, pistachio: 2, walnut: 6, almond: 1, pepper powder: 1, pepper paste: 1) out of 378 samples were screened as aflatoxin B1 positive by ELISA, but, 4 (1.1%; peanut: 2, pistachio:1, pepper powder: 1) out of the 22 samples screened were confirmed as aflatoxins positive at levels of 1.02~52.79 ng/g by LC/MS/MS. ELISA-LC/MS/MS system provides a more rapid, accurate and cost-effective method for the detection of aflatoxins in large number of samples.

• Journal of Food Hygiene and Safety
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• v.21 no.3
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• pp.153-158
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• 2006

The contamination levels of 3-MCPD(3-Monochloropropane-1,2-diol) and 1,3-DCP(1,3-Dichloro-2-Propanol) in soy sauce, sauces was monitored. 105 samples were collected from June 2005 to August 2005 in Gyeonggi-do. 3-MCPD and 1,3-DCP were analyzed by GCMSD. As results, the detection range of 3-MCPD concentration was between 0.02 mg/kg and 0.27 mg/kg in soy sauce. However any samples were not detected with 1,3-DCP. The contaminated rates of 3-MCPD in soy sauce was 17.1%. Soy sauce is the representative vegetable protein hydrolyzed food. The reliable analytical method f3r the toxic 3-MCPD and 1,3-DCP in Soy sauce has been studied. The derivatization studies of 3-MCPD and 1,3-DCP were performed mainly as Silylation with BSA(N,O-Bis(trimethylsilyl)-acetamide). The retention times of derivative, BSA-MCPD, BSA-DCP were 11.30 and 10.12 minutes.

• Journal of Food Hygiene and Safety
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• v.8 no.1
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• pp.9-15
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• 1993

In an attempt to quantitate and qualitate residual antibiotics and antibacterial agents in meat simultaneously, we studied a gas chromatography-mass spectrometry(GC/M8) analysis. For a simultaneous analysis of penicillin G, chloramphenicol and thiamphenicol in meat, a simple and rapid clean-up procedure including extraction with 0.01 M EDTA-2Na Mcilvaine buffer (pH 4.0), defatting with n-hexane, and elution with 0.01M-methanolic oxalic acid from Bond Elute $C_{18}$ cartridge, and quantitation by selected ion monitoring (SIM) mode after derivatization was performed. The recoveries (%) of penicillin G, chloramphenicol and thiamphenicol (CV, %) at 1 ppm fortification level were 63.5 (7.6), 76.3 (8.1) and 84.7 (2.0), and the detection limits of those were 0.6, 0.085 and $0.084\;\mu\textrm{g}$ beef, respectively. This method using 81M mode allows excellent detection and quantitation of residual antibiotics and antibacterial agents in meat. Moreover, confirmation by a full scan electron impact mass spectrum is possible if residual level in the sample in above 1 ppm.

• Journal of The Korean Society of Grassland and Forage Science
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• v.26 no.1
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• pp.45-52
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• 2006

This study was carried out to explore the accuracy of Near Infrared Reflectance Spectroscopy (NIRS) fer the prediction of digestibility and energy value of corn silages. The spectral data were regressed against a range of digestibility and energy parameters using modified partial least squares(MPLS) multivariate analysis in conjunction with first and second order derivatization, with scatter correction procedure(SNV-Detrend) to reduce the effect of extraneous noise. Calibration models for NIRS measurements gave multivariate correlation coefficients of determination$(R^2)$ and standard errors of cross validation of 0.92(SECV 1.73), 0.91(SECV 1.13) and 0.93(SECV 1.74) for in vitro dry matter digestibility(IVDMD), in vitro true digestibility(IVTD), and cellulase dry matter digestibility(CDMD), respectively. The standard error of prediction(SEP) and the multiple correlation coefficient of validation$(R^2v)$ on the validation set(n=39) was used in comparing the prediction accuracy. The SEP value was 0.30(TDN), 0.01(NEL), and 0.01(ME). The relative ability of NIRS to predict digestibility and energy value was very good for CDMD, total digestible nutrients(TDN), net energy fer lactation(NEL) and metabolizable energy(ME). This paper shows the potential of NIRS to predict the digestibility and energy value of con silage as a routine method in feeding programmes and for giving advice to farmers.

• Analytical Science and Technology
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• v.26 no.1
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• pp.19-26
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• 2013

Gibberllic acid ($GA_3$) is one of gibberellins (GAs) that are a class of plant growth hormones that exert profound and diverse effects on plant growth and development. $GA_3$ is essentially non-UV absorbing and is difficult to assay by UV-detector. For effective extraction of gibberellic acid from fruits by using liquid-liquid extraction, optimized pH and extraction solvent were established. The selective and sensitive derivative of $GA_3$ for HPLC/UV-vis was derivatized using phenacyl bromide, and the experimental factors, including reaction time, reaction temperature and amount of derivatizing reagent and base were investigated for the effective synthesis. The derivatized $GA_3$ with phenacyl bromide was effectively analyzed by HPLC/UV-vis. The structure of derivatized $GA_3$ was confirmed by HPLC/ESI-MS. For apple, LOD and LOQ were 0.008 mg/kg and 0.027 mg/kg, respectively. For pear, LOD and LOQ were 0.003 mg/kg, 0.012 mg/kg, respectively. The established method can be applied to more effective analysis of $GA_3$ from plant and food.