• Proceedings of the Korean Environmental Health Society Conference
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• 2004.06a
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• pp.169-172
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• 2004

A gas chromatography/mass spectrometric assay method was developed for the determination of propylene oxide adduct, N-(3-hydroxypropyl)valine. Adduct was released from hemoglobin by alkaline hydrolysis and extract at pH 8 with ethyl ether. The dried extract was completely derivatized with N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA)/TMS-I (100:3). The detection limits of the assay were 0.08 ng/g for N-(3-hydroxypropyl)valine based upon assayed hemoglobin of 0.1 g. The method was applied to the determination of propylene oxide adduct formed in young female Sprague-Dawley rats after treatment for 1, 2 and 3 weeks with 0.008 % propylene oxide via the drinking water. An adduct was detected by proposed procedure. The structure of the adduct could be assigned to N-(3-hydroxypropyl)valine.

• Journal of the Korean Applied Science and Technology
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• v.27 no.3
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• pp.337-343
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• 2010

1-Deoxynojirimycin(1-DNJ) was hardly detected by general UV detector. Therefore, in this study, we analyzed 1-DNJ, a effective functional material in which was contained the leaves of Cudrania tricuspidata and its tea by gas-chromatography. Synthesized a TMS derivative by attaching trimethylsilyl group to 1-DNJ, analyzed this by GC, and could detect a good peak. The leaves of Cudrania tricuspidata contains $1154.83{\pm}56.67$ ug/g.d.w of 1-DNJ and tea of Cudrania tricuspidata leaves does $8.01{\pm}0.61$ ug/g.d.w. This means the contents of 1-DNJ was nearly identical to each other. The larger size of the leaves had the more contents of 1-DNJ and the middle region of collection was the highest than any other collective regions of leaves.

• Journal of The Korean Society of Inherited Metabolic disease
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• v.15 no.3
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• pp.138-146
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• 2015

Purpose: If early diagnosis is not made, patients with metabolic disorders as homocystinemia rapidly progress to physical defect or mental retardation resulted in storage of the toxic material into the brain. Therefore, it is necessary to develop an analytical method for a rapid screening and/or correct confirmation diagnosis. Methods: The standard solution of sulfur amino acids spiked plasma was subjected to protein precipitation with methanol, and then consecutively derivatized with trimethylsilyl (TMS) and trifluoroacyl (TFA) and determined by GC-MS. The formation of TMS derivative of the hydroxyl and TFA derivative of amino functional group was performed by BSTFA and MBTFA, respectively. Selective ion monitoring (SIM) mode was used for quantification with selected specific ions. Results: A calibration curve on standard spiked pooled plasma showed a linear relationship with correlation coefficient of 0.9936-0.9992 for all compounds over the range of 0.1-300 ng. The precision and accuracy were within S.D. of 1-15% and RSD of 1-15% for intra-day assay at 2 ng/mL, 15 ng/mL and 30 ng/mL. LOD and LOQ was 0.4 ng/mL and 4 ng/mL respectively. Conclusion: A rapid analytical method was developed to quantify sulfur amino acids and methyl malonic acid, after two-step derivatization procedure with good sensitivity and specificity on human plasma. Advantages of a new method are simplicity and rapidity. The method could be useful for routine analysis, diagnosis of homocysteinemia.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1497-1504
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• 2009

GC/MS analysis of catecholamines (CAs) in biological sample may produce poor reproducible quantitaion when chemical derivatization is used as the technique to form a volatile derivative. Significant quantities of the side products can be formed from CAs with primary amine during the derivatization reaction under un-optimized conditions. We have tested various chemical derivatization techniques in an attempt to find an optimum derivatization method that will reduce side product formation, enable to separate several catecholamine derivatives in GC chromatogram, and obtain significant improvement of detection sensitivity in GC/MS analysis. Whereas several derivatization techniques such as trimethylsilylation (TMS), trifluoroacylation (TFA), and two step derivatization methods were active, selective derivatization to form O-TMS, N-heptafluorobutylacyl (HFBA) derivative using N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) and N-methyl-bis(heptafluorobutyramide) (MBHFBA) reagents was found to be the most effective method. Moreover, this derivative formed by selective derivatization could provide sufficient sensitivity and peak separation as well as produce higher mass ion as base peak to use selected ion in SIM mode. Calibration curves based on the use of an isotopically labeled internal standard show good linearity over the range assayed, 1 ~ 5000 ng/mL, with correlation coefficients of > 0.996. The detection limits of the method ranged from 0.2 to 5.0 ppb for the different CAs studied. The developed method will be applied to the analysis of various CAs in biological sample, combined with appropriate sample pretreatment.

• Archives of Pharmacal Research
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• v.20 no.3
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• pp.247-252
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• 1997

Perfluorotolyl (PFT)-ether and perfluorotoly-trimethylsilyl (PFT-TMS) ether derivatives of oestrone, $17{\alpha}$- and $17{\beta}$oestradiol were prepared under phase transfer conditons. The former derivatives under negative ion chemical ionization conditions gave significant ions in the mass spectrometer but $17{\alpha}$- and $17{\beta}$ -oestradiol gave poor resolution. However, the PFT-TMS derivatives of 17.${\alpha}$- and$17{\beta}$-oestradiol showed good resolution. These derivatives were used for the analysis of oestrogens in bovine aqueous humour, vitreous humour and retina. The mean $({\pm}SEM)$ concentrations of oestrone in bovine aqueous humour (n=18), vitreous humour (n=18) and bovine retina (n=4) were $0.47{\pm}0.11$, $0.46{\pm}0.14$ and $1.10{\pm}0.24 ng.ml^{-1}$, respectively. $17{\alpha}$-Oestradiol was detected in 16 out of 18 samples of bovine aqueous humour and vitreous humour and the mean $({\pm}SEM)$ concentrations were $0.30{\pm}0.10$ and $0.08{\pm}0.02 ng.ml^{-1}$, respectively. The mean $({\pm}SEM)$ concentration of 17.betha.-oestradiol in aqueous humour (n=7) and vitreous homour (n=11) $0.83{\pm}0.26 ng ml^{-1}$ and $0.39{\pm}0.09 ng ml^-1$, respectively. In retina the concentrations of both steroids were below the detection limit.

• Analytical Science and Technology
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• v.28 no.5
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• pp.323-330
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• 2015

Alkaptonuria, a rare inherited metabolic disease, is characterized by a lack of homogentisate dioxygenase and accumulation of homogentisic acid (HGA), leading to homogentisic aciduria, arthritis, and ochronosis. In this study, a rapid analytical method, without an expensive and tedious solid phase extraction step, was developed to quantify HGA in plasma using GC-MS. HGA-spiked pooled plasma samples were subjected to liquid-liquid extraction (LLE) with ethyl acetate, followed by trimethylsilyl derivatization (TMS) and GC-MS quantification using selected ion monitoring. The formation of TMS derivative of the 1 carboxylic and 2 hydroxyl functional groups was performed by reacting BSTFA (with 10% TMCS) for 5 min at 80 ℃. For selected ion monitoring, quantification and confirmation ions were determined based on specific ions (m/z 384, m/z 341 and m/z 252) of the TMS derivative of HGA. Calibration curves of pooled normal plasma specimens showed a linear relationship in the range of 1-100 ng/µL. The precision and accuracy were within a relative standard deviation (RSD) of 1 to 15% and a bias of -5 to 25%. Recoveries were obtained in the range of 99-125% and 95-115% for intra-day and inter-day assay, respectively, at 2, 20 and 80 ng/µL. The limit of detection (LOD) and limit of quantification (LOQ) were 0.4 ng/µL and 4 ng/µL, respectively. No homogentisic acid was excreted from normal Korean plasma samples. Collectively, the results from the present study suggest that this method could be useful for routine diagnosis and therapeutic monitoring of alkaptonuria patients with excellent sensitivity and rapidity.

• Analytical Science and Technology
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• v.11 no.5
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• pp.374-385
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• 1998

Phytoestrogens are biologically active compounds derived from plants foods. It had been suggested that phytoestrogens, by inhibiting aromatase in peripheral and/or cancer cells and lowering estrogen levels, may play a protective role as antipromotional compounds during growth of estrogen-dependent cancers. Therefore, simultaneous analysis of estrogens and phytoestrogens is necessary to elucidate the possible involvement of phytoestrogens in estrogen metabolism. In this view, we developed a simple and reproducible procedure to quantitatively determine estrogen and phytoestrogen metabolites. The proposed method consisted of solid phase extraction using preconditioned Serdolit AD-2 resin, enzyme hydrolysis with ${\beta}$-glucuronidase/arylsulfatase from Helix pomatia, liquid-liquid extraction and TMS-ether derivatization. And the final determination was carried out by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring mode (SIM). The precision and accuracy of this method was evaluated through within-a-day and day-to-day test. Recovery range and detection limit were 71.96~105.66%, 2~4 ng/mL, respectively. Using this method, 17 estrogen and 5 phytoestrogen compositions in urine of normal subjects were analyzed. It was found that amounts and relative distribution of urinary phytoestrigens and estrogens showed different pattern in male and female subjects.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.30 no.3
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• pp.355-360
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• 1997

In order to investigate the influence of photosensitized oxidation in the sun-dried irish moss (Chondrus Ocellatus), laver (Porphyra Yezoensis) and ultra violet irradiated oyster (Crassostrea gigas) the oxidation of lipid and isomers of hydroperoxides were analyzed by gas chromatography-mass spectrometry. The lipid contents of oyster, irish moss and layer were $2.7\%,\;0.1\%,\;0.1\%$ of respectively. Peroxide value, 56,7 meq/kg in the raw oyster was increased of 100.9 meq/kg by the U.V, irradiation for 4 hours. Also the peroxide values of the irish moss and laver were increased by the sun-drying. In the identification of hydroperoxides isomers by trimethylsily (TMS) derivative of photo-oxidized lipid from oyster, irish moss and laver, the proportions of positional isomer, 9-OOH and 13-OOH were dominant than those 10-OOH and 12-OOH.

• Journal of the Korean Chemical Society
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• v.42 no.3
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• pp.266-276
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• 1998

Cholesterol supersaturation in bile, which causes gallstone formation, is the result of low bile acid secretion or high cholesterol secretion. The quantitative analysis of cholesterol, bile acids and sterols which are precursors of cholesterol have been used to examine the changes in bile component. We described a simple, sensitive and reproducible method for simultaneous determination of cholesterol, five bile acids and seven sterols in human bile juices and gallstones by capillary column gas chromatography-mass spectrometry (GC/MS). Clinical samples were hydrolyzed by alcoholic KOH, extracted twice (pH 14 and 1) and derivatized to trimethylsilyl (TMS) ether with $MSTFA/NH_4I$ (N-methyl-N-trimethylsilyltrifluoroacetamide/ammonium iodide) mixture in order to be detected on the GC/MS. The good quality control data were obtained through within-a-day and day-to-day test (RSD values were 1.72-13.79, 0.68-14.10, respectively) and the recovery range of them was 73.56-96. 95 Using this method, biliary and gallstone compositions in the patients with intrahepatic stones were analyzed. The amounts and its relative distribution of cholesterol, bile acids and sterols showed different pattern in bile juices and gallstones.

• Korean Journal of Food Science and Technology
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• v.39 no.4
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• pp.360-365
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• 2007

The studies for the derivatization of 3-monochloropropane-1,2-diol (3-MCPD) were performed mainly as acylation with HFBI (heptafluorobutyrylimidazole), alkylation with PBA (phenylboric acid) and silylation with BSTFA (N,O-bis[trimethylsilyl]trifluoroacetamide). Also silylation with MTBSTFA(N-methyl-N-[tert.-butyldimethylsilyl] trifluoroacetamide) and acylation with MBTFA (N-Methyl-bis[trifluoro-acetamide]) were also considered. Except the TBDMS derivative of 3-MCPD, all the derivatives were detected well. The derivatives of 3-MCPD with HFBI, PBA and BSTFA showed below 10 ${\mu}g/kg$ which was sensitive enough to satisfy Korea maximum residue limit 0.3 mg/kg. Among the tested adsorbents, Extrelut20 and Florisil were evaluated as the proper adsorbents to eliminate the soy sauce matrix for 3-MCPD. Ethyl acetate was the most efficient eluent with good recovery rate. The desired surrogate compound and internal standard were 1,2-butanediol and 1,2-dibromo-3-chloropropane, respectively. The limit of detection for PB-MCPD and TMS-MCPD were 10.16 and 7.06 ${\mu}g/kg$ on GC/MSD, respectively. HFB-MCPD derivative showed the lowest detection limits 2.98 and 5.32 ${\mu}g/kg$ by GC/ECD and GC/MSD, respectively.