• 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.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1396-1398
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• 2003

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.348-354
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• 2009

Copper(II) complexes with tetraoxo dithia tetraaza macrocyclic ligands; [18]ane$N_4S_2$: 1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, [20]ane$N_4S_2$: 1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane,Bzo2[18]ane$N_4S_2$: dibenzo-1,4,10,13-tetraaza-5,9,14,18-tetraoxo-7,16-dithia-cyclooctadecane, Bzo2[20]ane$N_4S_2$: dibenzo-1,5,11,15-tetraaza-6,10,16,20-tetraoxo-8,18-dithia-cyclocosane; were entrapped in the nanopores of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)copper(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); $[Cu(N-N)_2]^{2+}$-NaY; in the nanopores of the zeolite, and (ii) in situ template condensation of the copper(II) precursor complex with thiodiglycolic acid. The obtained complexes and new host-guest nanocomposite materials; $[Cu([18]aneN_4S_2)]^{2+}-NaY,\;[Cu([20]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[18]aneN_4S_2)]^{2+}-NaY,\;[Cu(Bzo_2[20]aneN_4S_2)]^{2+}$-NaY; have been characterized by elemental analysis FT-IR, DRS and UV-Vis spectroscopic techniques, molar conductance and magnetic moment data, XRD and, as well as nitrogen adsorption. Analysis of data indicates all of the complexes have been encapsulated within nanopore of zeolite Y without affecting the zeolite framework structure.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.17 no.2
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• pp.81-88
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• 2007

The aim of this study was to investigate whether the exposure to vinyl chloride monomer(VCM) induces lipid peroxidation in workers by evaluating the concentration of malondialdehyde(MDA) in the urine in order to assess worker's oxidative stress due to exposure of vinyl chloride monomer. The subjects investigated in the study were divided into the experimental group; 18 workers exposed to VCM, and the control group; 19 workers unexposed to VCM. A gas chromatography/pulsed flame photometric detector(GC/PFPD) was utilized to analyze thiodiglycolic acid(TDGA), which was methylated with trimethylsilyldiazomethane (2.0M in diethyl ether) in urine and the urinary MDA, the product of lipid peroxidation, was determined by high-performance liquid chromatography/ultraviolet-visible detector after derivatized with 2,4-dinitrophenylhydrazine(DNPH). The concentrations of urinary TDGA in controls and VCM exposure workers were 0.13(2.01)mg/g Cr. GM(GSD) and 0.35(1.96)mg/gCr. GM(GSD), respectively. The concentrations of urinary MDA were $0.12(2.21){\mu}mol/gCr$. GM(GSD) in controls and $1.35(1.79){\mu}mol/gCr$. GM(GSD) in VCM exposure workers. As a result of simple regressions analysis between urinary concentration of TDGA and MDA in VCM exposure workers, it was found that the $R^2$ value was 0.261 (p=0.03) and the drinking and smoking did not affect their level. In conclusion, the workers exposed to VCM have a potentially to suffered by oxidative stress due to VCM exposure and the urinary MDA can be applicable to the marker of effect to assess the level of worker's VCM exposure.