• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.529-536
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• 2005

Measurement of toxicologically relevant polychlorinated biphenyl (PCB) congeners such as non-ortho(IUPAC#) 77, 81, 126, 169 and mono-ortho 105, 114, 118, 123, 156, 157, 189 and di-ortho 170, 180 and polybrominated diphenyl ethers (PBDEs) such as 47, 66, 85, 99, 100, 138, 153, 154 in environmental samples become almost mandatory in several countries now. However, most of the available methods involve expensive instrumentations such as HRGC-HRMS or ECNI-LRMS, apart from expensive extraction and clean-up (with large volume of solvents) steps. A method has been devised combining the analytical separation power of PYE [2-(1-pyrenyl)ethyldimethysilylated silica] column HPLC and high-resolution gas chromatographic techniques including micro-electron capture detection (ECD) and two dimensional gas chromatograpy-ECD techniques to determine these eco-toxic substances at parts-per-trillion (ppt) levels. This combination resolves co-elution of congeners that occur in disproportionate ratios (e.g. CB-110 and -77) and allows accurate congener-specific determination of target compounds. This method is cost effective as it requires only hexane, that in small quantities (10 mL) and GC-ECD. The elution and analysis time are optimized to less man hours. This method is effectively utilized in the analysis of co-planar PCBs and PBDEs from archived solvent extracts of samples previously analyzed for pesticides and PCBs. Structure based separation of contaminant classes improves GCECD determination at ppt levels.

• YAKHAK HOEJI
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• v.55 no.4
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• pp.277-283
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• 2011

Simultaneous monitoring of catecholamines and serotonin with their appropriate extraction from the biological samples is required in order to understand thoroughly the regulation of the central and peripheral nervous system. In the present research the segmented gradient elution with the solid phase extraction using a C18 cartridge rather than the previous isocratic elution with alumina extraction is successfully employed to determine norepinephrine (NE), epinephrine (E), dopamine (DA), serotonin (5HT), 3,4-dihydroxyphenylacetic acid (DOPAC) and 5-hydroxyindoleacetic acid (5HIAA) simultaneously within 20 minutes using 3,4-dihydroxyhydrocinnamic aicd as the internal standard (IS). Linearities were obtained in the concentration range between $5{\times}10^{-6}M$ and $1{\times}10^{-4}M$ for all 7 compounds with detection limits of 0.6~1.9 ${\mu}M$. The present HPLC/ECD method yielded reasonable accuracy (relative error; -1.4~1.1%) and precision (relative standard deviation; 0.4~1.9%) for 9 measurements of the standard solution consisting of NE, E, DA, 5HT, DOPAC and 5HIAA compounds. Recoveries of catecholamines, serotonin and their metabolites from human serum were in the range of 57%~86%. While the concentrations of NE and 5HT in the serum of normal Sprague-Dawley rat were found as $1.4{\times}10^{-6}M$ and $2.6{\times}10^{-6}M$, respectively, the contents of NE and 5HT in the serum of the stressed rat were increased 5.6 times and 1.4 times more, respectively.

• The Korean Journal of Pesticide Science
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• v.16 no.3
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• pp.242-256
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• 2012

QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method has been a lot of research for pesticide analysis, because it is very simple and fast. However, this method requires high sensitivity instrument such as LC-MS/MS because of the use of small sample volume and many impurities compared to the conventional method. So, QuEChERS method needs to be modified for using with HPLC and GC-ECD/NPD. The aim of this work was to study the application of the QuEChERS method as well as its modification for the extraction and preconcentration of 5 groups of 61 pesticides from 4 fruits prior to their determination by HPLC-PDA, GC-ECD/NPD, and LC-MS/MS. The method was validated using spiking levels at 0.1 mg/kg (or 0.01 mg/kg) in apple, grapes, pear and persimmon. The average recovery by QuEChERS AOAC Official 2007. 01 version using the LC-MS/MS varied from 71.1127.4% for 61 pesticides. The average recovery rates using modified QuEChERS varied from 70.9~126% for 61 pesticides by HPLC-PDA and GC-ECD/NPD. The results satisfied the criteria of multiple pesticide residue analysis, setting 70~130% for recovery rates and below 30% for CV.

• Proceedings of the Ginseng society Conference
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• 2002.10a
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• pp.238-252
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• 2002

In order to screen out indicators for the discrimination of ginseng habitat, some physical and chemical characteristics of Korean red ginsengs (94 kinds) and Chinese red ginsengs (50 kinds) were analyzed by using a rheometer, an electronic nose system, a combined technique of solid phase micro-extraction (SPME) and gas chromatograph equipped with an electron capture detector (GC/ECD), an X-ray fluorescence spectrometer (XRF), an inductively coupled plasma mass spectrometer (ICP/MS), a near infrared spectrometer (NIRs) and high performance liquid chromatography equipped with evaporative light scattering detector (HPLC/ELSD). The results are summarized as follows: (i) The rhizome strengths of Korean red ginsengs were significantly higher than those of Chinese red ginsengs. (ii) The electronic nose patterns of Korean red ginsengs were significantly different from those of Chinese red ginsengs. (iii) Some unidentified peaks were detected not in the headspace of Korean red ginsengs but in the headspace of Chinese red ginsengs when the headspace volatiles prepared by the SPME technique were analyzed by GC/ECD. (iv) Either the content ratios of K to Ca or Mn to Fe were significantly different between Korean red ginsengs and Chinese red ginsengs. (v) The reflectance ratios of NIRs wavenumbers such as $904\;cm^{-1}\;to\;1088\;cm^{-1}$ for Korean red ginsengs were significantly different from those for Chinese red ginsengs. (vi) The content ratios of ginsenoside-Rg to ginsenoside-Re of Korean red ginsengs were significantly higher than those of Chinese red ginsengs. These results indicate that the rhizome strength, the electronic nose pattern, the occurrence of ECD-sensitive headspace volatile components, the content ratios of K to Ca and Mn to Fe, the NIRs pattern and the content ratio of ginsenoside-Rg to -Re may be indicators for the discrimination of ginseng habitat.

• Analytical Science and Technology
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• v.8 no.2
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• pp.215-220
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• 1995

A simple, efficient and sensitive method was described for the simultaneous determination of catecholamine, indoleamine and related metabolites from the homogenates of the rat brain striatum by HPLC-ECD. The optimum mobile phase on a reverse phase $C_{18}$ column was 35mM sodium acetate buffer(included 10mM citric acid, 0.13mM $Na_4EDTA$, 0.58mM SOS, pH3-4):MeOH=85:15. The column temperature was $30^{\circ}C$. Dopamine(DA), 3, 4-dihydroxyphenyl acetic acid(DOPAC), homovanilic acid(HVA), 5-hydroxyindole acetic acid(5-HIAA), serotonin(5-HT) and noradrenaline(NA) could be separated and analysed to very small amount. The detection limits of this method were 2~10pg per injection for all components. The effects of age and sex of rat on the contents of the catecholamines and their metabolites in rat brain striatum were studied. The levels of DA and 5-HT contents of the 7 week old female rats were higher than those of the 7 week old male rats. As the age of rat increases, the contents of DOPAC increased significantly.

• Analytical Science and Technology
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• v.8 no.4
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• pp.887-894
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• 1995

Toward the development of universal, sensitive, and convenient method of DNA (or RNA) detection, two kinds of electrochemically active DNA ligands. acridine - viologen and oligonucleotide - ferrocene conjugate, were prepared. Thermodynamic and electrochemical study revealed that these probes bound strongly to DNA, and showed a typical cyclic voltammograms, indicating a potential for use as a reversible electrochemical labelling agent for DNA. Especially, using the electrochemically active oligonucleotide, we have been able to demonstrate the detection of DNA at femtomole levels by HPLC equipped with ordinary electrochemical detector (ECD). These results lead to the conclusion that the redox-active probes are very useful for the microanalysis of nucleic acid due to the stabilily of the complexes, high detection sensitivity, and wide applicability to the target structures (single- and double strands) and sequences.

• YAKHAK HOEJI
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• v.43 no.3
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• pp.300-305
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• 1999

A sensitive and efficient assay method was applied to determine the level of glutamic acid (GA) and ${\gamma}-aminobutyric$ acid (GABA) in frontal cortex and hippocampus of rat administrated with ethanol and drugs. The compounds were derivatized with ο-phthalaldehyde (OPA) and 2-mercaptoethanof for precolunm analysis. The condition for the simultaneous determination of GA, GABA and $\beta-aminobutyric$ acid (BABA) by high performance liquid chromatography with electrochemical detection was reverse phase $C_{18}$ column as stationary phase, 0.1 M phosphate buffer containing 0.1 mM $Na_4EDTA$ : methanol = 55:45 (v+v) pH 3.8 as mobile phase and 0.7V electrode voltage. The stability of reaction product of GA, GABA and BABA with OPA could be increased by adding the same volume of polyethylene glycol 400 to reaction mixture. The GABA level in frotal cortex of rat was significantly decreased by the administration of picrotoxin and diazepam, but it was significantly increased by the administration of red ginseng total saponin, N-methyl-D-glucamine and (-)-deprenyl.

• Korean Journal of Environmental Agriculture
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• v.29 no.3
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• pp.257-265
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• 2010

In this study, the residual levels of four insecticidal compounds (lambda-cyhalothrin, lufenuron, thiamethoxam, and clothianidin) were monitored in the pomegranate, in order to assess the risk to consumers posed by the presence of such residues. The insecticides were applied at the recommended dose rates onto pomegranate trees. The samples were then collected at harvesting time after several treatments (two, three, and four treatments). After sample preparation progressed through the clean-up procedure, lufenuron, thiamethoxam, and clothianidin residues were analyzed via a HPCL-UVD, and the lambda-cyhalothrin residue was analyzed via a GC-${\mu}ECD$. The versatility of this method was evidenced by its excellent linearity (>0.9998 to 1) at broad concentration ranges. The mean recoveries evaluated from the untreated sample spiked with two different fortification levels ranged from 72.45 to 113.90%, and the repeatability (as a relative standard deviation) resulted from triplicate recovery tests was in a range from 0.80 to 11.75%. The residues of all insecticides determined from treated pomegranate samples and their LOD levels (lunfenuron, 0.01; lambda-cyhalothrin, 0.005; thiamethoxam, 0.01; clothianidin, 0.02 mg/kg) were much lower than their MRLs (0.5 mg/kg).

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.6 no.1
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• pp.28-37
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• 1996

Benzidine, an aromatic amine used primarily in the manufacture of azo dyes, is recognized as a urinary bladder carcinogen in humans. In rats, mice, and hamsters, chronic exposure to benzidine resulted in tumors of the liver. The present study was undertaken to suggest analyzing the metabolites of benzidine with the optimal condition, identify the metabolites of benzidine, and observe time variance of the metabolites in the isolated perfusated rat liver. N-acetylbenzidine was synthesized by acetylation of benzidine with acetic anhydride and separated by thin layer chromatography(TLC) and high performance liquid chromatography(HPLC). To analysis benzidine and the metabolites of benzidine, HPLC operating condition has been optimized by means of preliminary experiment. The mobile phase consisted of acetonitrile(37%) in phosphate buffer, flow rate maintained at 1.0 ml/min. Optimal detective conditions were electrochemicaldetector(ECD) at 0.75 V for benzidine and N-acetylbenzidine and ultravioletdetector(UVD) at 287 nm for N,N'-diacetylbenzidine. The separation system was composed of a guard column and a separation column(Polymer C18, $4.6{\times}250cm$) at a temparature of $40^{\circ}C$. The perfusion system was equilibrated for 30 minutes before addition of benzidine to the perfusate. Samples of the perfusate were collected at time intervals(0, 10, 20, 30, 60, 90, 120 min) during the 2 hour perfusion. Before analyzing samples by HPLC/ECD/UVD, samples had been treated with sep-pak. Samples of perfusate analyzed by HPLC/ECD/UVD and the metabolites of benzidine in the isolated perfused rat liver were N-acetylbenzidine and N,N'-diacetylbenzidine. Benzidine metabolized over 60% during the initial 30 minutes of perfusion, extensively by 1 hour, and was undetectable in the perfusate. N-acetylbenzidine increased by 30 minutes of perfusion, declined. N,N'-diacetylbenzidine increased the 0-90 minutes period, remained constant during the 90-120 minutes period.

• The Korean Journal of Pesticide Science
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• v.11 no.2
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• pp.106-116
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• 2007

Pesticide, chlorfluazuron was subjected to determine the safety of terminal residues at the harvesting date of perilla leaves cultivated in plastic house. After the pesticide applied on a foliar spray in 2005 and 2006, leaf persistence of its residue was analysed for 10 days before leaf harvest. The degradation rate of chlorfluazuron in the leaf was 32.3 %(standard application), 43.6 %(double application) and 78.0 %(standard), 80.4 %(double) at second and tenth day, respectively, under analysis of GC/ECD in 2005. The degradation rate of chlorfluazuron in the leaf was 33.1 %(GC/ECD analyze), 34.0 %(HPLC/UVD analyze) and 77.9 %(GC/ECD), 78.4 %(HPLC/UVD) at second and tenth day, respectively, under the standard level of pesticide in 2006. The biological half-life of the chlorfluazuron residue was estimated by the regression equation calculated from daily dissipation of pesticide in the perilla leaves. The longest half-life of the chlorfluazuron residue in perilla leaves was 5.5 days. The maximum residual limit(MRL) for chlorfluazuron based on the longest half-life was estimated 2.0ppm at harvesting day, 2.5ppm at second day and 7.1ppm at tenth day before leaf harvesting of perilla.