• 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.

• Applied Chemistry for Engineering
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• v.10 no.8
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• pp.1169-1174
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• 1999

2-Diazo-1-naphthoquinone-5-sulfonyl chloride(NQD-Cl) was synthesized from sodium 2-diazo-naphthoquinone-5-sulfonate by chlorination. NQD-Cl was esterified with hydroxybenzophenones to give several 1,2-naphthoquinone-(2)-diazide-5-sulfonic acid ester derivatives(NQD-esters). We have compared benzophenone derivatives with methoxy group to benzophenone derivatives with hydroxy group. Solubility of each NQD-ester was studied. Each of NQD-esters was formulated with novolac base resin and PS plates were manufactured. Photosensitivity, bleachability, compatible exposed time and relative sensitivity were determined by UV spectrophotometry, imaged by UV lithographic techniques, and the gray scale method. According to the number of substituted NQD group, it showed that relative sensitivity was different from gray scale method. NQD-esters with methoxy group showed a good solubility and higher sensitivity than commercial PS ones.

• Korean Journal of Food Science and Technology
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• v.30 no.1
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• pp.125-131
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• 1998

The change of pectinesterase (PE) activity and pectin substances in fig fruit were investigated and low sugar jams prepared by various methods from fig fruit were compared. Fig fruit PE, which began to show the activity at the harvest time, was not inactivated and had slight activity during frozen storage at $-25^{\circ}C$. The amount of alcohol insoluble solid (AIS) and the degree of esterification (DE) of AIS were reduced by its own PE activity. However the intrinsic PE of fig fruit was not enough to make low-methoxyl pectin below 50% of DE. Fig pulp treated by its own PE and combination of fig PE and orange PE could make low-methoxyl pectin. After PE treatments, fig pulp adjusted below pH 4.0 by addition of citric acid kept red colour. Fig Jams processed by various methods had lower soluble solid $(31{\sim}49^{\circ}Brix)$ compared with conventional fig jam. Five kinds of fig jams out of those showed higher score than others in the sensory evaluation. For preparation of the five jams, the fig pulps with or without 1% pectin were treated at $50^{\circ}C$ for 25 minutes with addition of orange PE (200 units/400 g pulp). The treated pulps were added with 0.25% citric acid, 0.7% calcium and 20% cane sugar. The mixed pulps were prepared for jams containing low sugar by hot plate or microwave or refrigeration (excepting the mixed pulp without pectin).

• Applied Biological Chemistry
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• v.35 no.2
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• pp.110-114
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• 1992

The lipid compositions, physical and chemical characteristics of crude oil in Korean safflow, Carthamus tinctorius L., seeds were determined and proxmate composition of it were also analyzed. The proximate composition showed moisture 7.2%, carbohydrate 34.4%, crude protein 18.2%, crude fat 34.8% and ash 5.35. Specific gravity, refractive index, smoking point, melting point and titer of the crude oil were $0.922{\sim}0.927,\;1.468{\sim}1.469,\;210^{\circ}C,\;-15{\sim}-18^{\circ}C\;and\;15{\sim}18$, respectively. Iodine value, saponification value, acid value, esterification value, unsapoifiable matter and saturated fatty acid content of the crude oil were $140{\sim}152,\;186{\sim}192,\;2.6{\sim}3.5,\;179{\sim}186,\;0.8{\sim}1.3%\;and\;6.6{\sim}7.2%$, respectively. Fatty acid compositions were quantitatively determined by G.L.C. to give $70{\sim}78%$ linoleic acid, $10{\sim}23%$ oleic acid and $5{\sim}8%$ palmitic acid as main components, stearic, linolenic and myristic acid were presented in small quantities.

• Korean Journal of Environmental Agriculture
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• v.13 no.2
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• pp.199-208
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• 1994

Analytical methods for the determination of the derivatives of the herbicide (${\pm}$)-2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) by capillary column gas chromatography with mass spectrometer (GC-MS) and electron-capture detection (GC-ECD) were studied. A successful procedure was introduced for the ester preparation using $H_2SO_4$, as the catalyst and the alcohol 2,2,2-trichloroethanol (TCE) or 2,2,2-trifluoroethanol (TFE). The identificaiton and elucidation of MCPP by GC-MS spectrometry following the esterification with diazomethane, $BF_3$/methanol, $H_2SO_4$/methanol, TCE, TFE, or pentafluorobenzyl bromide (PFB) were carried out. A comparison of the response-sensitivities among those MCPP esters was made with GC-ECD. Although the methylation product of MCPP was confirmed by GC-MS, its low sensitivity to the ECD limited the detection of MCPP. TCE, TFE, and PFB derivatization methods resulted in a high rate of MCPP esterifications and very sensitive ECD molecular responses. Based on efficiency, convenience, worker safety, and least sample contamination, TFE esterificaiton was considered as the superior method for MCPP analysis to the other methods of derivatization. An accurate method is described for quantifying MCPP in soil leachates by GC-ECD at very low concentrations without the requirement of a complicated clean-up process. As a result, MCPP residues at concentrations of less than $0.1{\mu}g$ in 100ml soil leachate were detected.

• The Korean Journal of Nuclear Medicine
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• v.31 no.4
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• pp.440-451
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• 1997

This study was designed to prospect the $^{111}In$-labelled paclitaxel as tumor imaging agent. In order to provide a taxol molecule with a functional group which is able to chelate In-111, taxol-DTPA conjugate and 2'-hemisuccinyltaxol were synthesized by esterification of taxol at C-2'on C-13 carbon with DTPA anhydride and succinic anhydride, respectively. Synthesis yield of the taxol derivatives was 34% for taxol-DTPA and 80% for 2'-hemisuccinyltaxol. Cytotoxicity of the taxol derivatives were measured by MTT method toward cell lines HT29, B16, P388, and CT26. The cytotoxic activities of the taxol derivatives were maintained, although less active than taxol. Radiolabelling of the taxol derivatives were proceeded directly with $^{111}InCl_3$ or indirectly with $^{111}In$-citrate(ligand-exchange method). The ligand-exchange method was not suitable because some precipitates appeared during the reaction. On the contrary, by direct radiolabelling method, we were able to obtain taxol-DTPA-$^{111}In$ in 100% radiochemical yield. However, 2'-hemisuccinyltaxol was not labelled by both methods. Yield and radiochemical purity of the radiolabelled com-pound were determined by HPLC, paper chromatography and instant thin layer chromatography. Taxol-DTPA-$^{111}In$ was characterized to be hydrophilic by lipophilicity test, and nearly non-adhesive to HT29, B16, P388, and CT26 by cell binding affinity test. Binding affinity of the taxol-DTPA-$^{111}In$ complex to serum proteins was also examined by protein precipitation with 30% trichloroacetic acid. The results showed that 30% of the taxol-DTPA-$^{111}In$ complex binds with serum proteins.

• Journal of Life Science
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• v.17 no.7 s.87
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• pp.910-914
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• 2007

In order to synthesize new bioactive compounds and contrasting agents, reactions of glycine and glutamic acid as an animo acid with paraformaldehyde and hypophosphorous acid were executed. Products are 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid 1 and 3,7-dihydroxy-3,7- dioxoperhydre-1,5,3,7-diazadiphosphocine-1,5-di-(2-glu taric acid) 3. 2-[5-(1,2-Dicarboxyethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7] diazadiphosphocan-1-yl]-succinic acid 2 by using aspartic acid was not obtained. Esterification of 3,7- dihydroxy-3,7-dioxoperkydro-1,5,3,7-diaza-diphosphocine-1,5-diacetic acid 1 by treatment of methanol, ethanol, and propanol were executed. 3,7-Dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3.7-dihydroxy-3,7-dioxoperhydro-1,5,3,f-diazadiphosphocine-1.5-diacetic acid ethyl ester 5, and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6 were respectively synthesized in good yields. Continuously, we will try synthesis of novel compounds and evaluation of biological activity.

• Membrane Journal
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• v.17 no.4
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• pp.311-317
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• 2007

Proton conducting crosslinked membranes have been prepared by polymer blending, which consist of poly(vinyl alcohol-co-ethylene) (PVA-co-PE) and poly(styrene sulfonic acid-co-maleic acid) (PSSA-co-PMA) at 50 : 50 wt ratio. Two kinds of PSSA-co-PMA copolymer with 3 : 1 and 1 : 1 the molar ratio of PSSA to PMA wereused as a proton conducting source. The ethylene content of PVA-co-PE was also changed as 0, 27 and 44 mol%. The membranes were thermally crosslinked via the esterification reaction between -OH of PVA and -COOH of PMA, as demonstrated by FT-IR spectroscopy (PVA-co-PE)/(PSSA-co-PMA) membranes with 3 : 1 the molar ratio of PSSA to PMA showed higher ion exchange capacity (IEC), lower water uptake and higher proton conductivity than those with 1 : 1 molar ratio. As the PE concentration increased, the IEC values, water uptake and proton conductivities decreased continuously. These properties were elucidated in terms of competitive effect between the concentration of sulfonic acid, hydrophilicity and the crosslinked structure of membranes.

• Membrane Journal
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• v.15 no.3
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• pp.206-212
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• 2005

Acid-resistant poly(vinyl alcohol) (PVA) membranes connected with ethylene and ether groups were prepared via a thermal crosslinking reaction by varying the ratio of PVA to ethylene glycol diglycidyl ether (EGDE). The crosslinked membranes were characterized using FT-IR and swelling tests, respectively. Pervaporation behaviors with the PVA membranes were investigated for aqueous TFEA (2,2,2-trifluoroethanol) as a function of EGDE content and operating temperature. The pervaporation properties far MA (methacrylic acid)/water mixture were also carried out with the optimized PVA membrane. The PVA membranes prepared with EGDE showed more excellent acid-resistance than those crosslinked with gluaraldehyde. The membranes showed high permeation fluxes of 0.1 and $0.3\;km^2h$ and high separation factors of 100 and 900 in the $96\;wt\%$ TFEA and MA aqueous fred mixtures at high temperature above $80^{\circ}C$, respectively. These confirmed theses membranes could be used in esterification membrane reactor process for the production of 2,2,2-trifluoroethylmetacrylate (TFEMA).

• Membrane Journal
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• v.19 no.4
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• pp.302-309
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• 2009

A block copolymer of polystyrene-b-poly (hydroxyl ethyl methacrylate), PS-b-PHEMA, was synthesized via atom transfer radical polymerization (ATRP) and crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via esterification of the -OH groups of PHEMA in the block copolymer and the -COOH groups of IDA. Upon doping with $H_3PO_4$ to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased as the content of $H_3PO_4$ increased. In addition, both the tensile strength and the elongation at break increased with IDA content. A proton conductivity of 0.01 S/cm at $100^{\circ}C$ was obtained for the PS-b-PHEMA/IDA/$H_3PO_4$ membrane with [HEMA]:[IDA]:[$H_3PO_4$] = 3:4:4 under anhydrous conditions. All of the PS-b-PHEMA/IDA/$H_3PO_4$ membranes were thermally stable up to $350^{\circ}C$, as revealed by thermal gravimetric analysis (TGA).