• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.26 no.2
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• pp.178-187
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• 2016

Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.

• Toxicological Research
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• v.14 no.4
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• pp.525-533
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• 1998

The covalent interactions of toluenediisocyanate (TDI) with macromolecules were investigated both in vitro and in vivo. In vitro incubations of 2,4- and 2,6-TDI with DNA or proteins resulted in dose-dependent formation of TDI-protein and TDI-DNA adducts. TDI-treated DNA was highly resistant to enzymatic digestion and thermal hydrolysis, but was readily hydrolyzed under acidic conditions by releasing its corresponding toluenediamine (TDA), suggesting that TDI caused the crosslinking of DNA. Reaction of TDI with albumin and globin resulted in the formation of several adducts, and some adducts were formed in blood of TDI-treated rats in a dose-dependent fashion. Administration of TDI to rats resulted also in a dose-dependent binding of TDI to hepatic tissue. Levels of TDI-albumin adducts were 10 times higher than those of TDI-globin adducts; the biological half lives of TDI-albumin and TDI-globin adducts were 1.2 and 12.5 days, respectively. Globin adducts were detected up to 28 days after the treatment. Hepatic TDI protein adducts were persistent for a substantial period whereas the levels of hepatic TDI-DNA adduct were decreased rapidly. These results indicate that the isocyanato group of TDI is not readily hydrolyzed under physiological conditions, is transported to other organs, and is bound to DNA and/or proteins without further metabolic activation. As the adducted products degrade in the body, TDA is released and introduced to the liver. TDA may additionally bind to hepatic tissue after metabolic activation. Thus, the toxic effect of TDI exposure is considered to persist during the lifetime of the adducted biological macromolecules.

• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.650-658
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• 2006

The recycling of TDA from solid waste of TDI plant(TDI-R) by near-critical hydrolysis reaction had been studied by means of a statistical design of experiment. The main and interaction effects of process variables had been defined from the experiments in a batch reactor and the correlation equation with process variables for TDA yield had been obtained from the experiments in a continuous pilot plant. It was confirmed that the effects of reaction temperature, catalyst type and concentration, and the weight ratio of water to TDI-R(WR) on TDA yield were significant. TDA yield decreased with increases in reaction temperature and catalyst concentration, and increased with an increase in WR. As a catalyst, NaOH was more effective than $Na_2CO_3$ for TDA yield. The interaction effects between catalyst concentration and temperature, WR and temperature, catalyst type and reaction time on TDA yield had been defined as significant. Although the effect of catalyst concentration on TDA yield at $300^{\circ}C$ as subcritical water was insignificant, the TDA yield decreased with increasing catalyst concentration at $400^{\circ}C$ as supercritical water. On the other hand, the yield increased with an increase in WR at $300^{\circ}C$ but showed negligible effect with WR at $400^{\circ}C$. The optimization of process variables for TDA yield has been explored with a pilot plant for scale-up. The catalyst concentration and WR were selected as process variables with respect to economic feasibility and efficiency. The effects of process variables on TDA yield had been explored by means of central composite design. The TDA yield increased with an increase in catalyst concentration. It showed maximum value at below 2.5 of WR and then decreased with an increase in WR. However, the ratio at which the TDA yield showed a maximum value increased with increasing catalyst concentration. The correlation equation of a quadratic model with catalyst concentration and WR had been obtained by the regression analysis of experimental results in a pilot plant.

• Journal of Food Hygiene and Safety
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• v.30 no.1
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• pp.81-86
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• 2015

The purpose of our paper was to investigate the migration level of 4,4'-MDA(4,4'-methylenedianiline), 2,4-TDA(2,4-toluenediamine), aniline, acrylonitrile and methylmeth acrylate from plastic cookwares into food simulants and to evaluate the safety of each monomers. The test articles for monomers were PA (polyamide) items for 4,4'-MDA, 2,4-TDA and aniline, PU (polyurethane) items for 4,4'-MDA, ABS (acrylonitrile-butadiene- styrene) items for acrylonitrile, and acrylic resin items for methylmethacrylate. All the article samples of 321 intended for contact with foods were purchased in domestic market. 4,4'-MDA, 2,4-TDA and aniline were analyzed by LC-MS/MS (liquid chromatography -tandem mass spectrometer), acrylonitrile by GC-NPD (gas chromatography-nitrogen phos phorus detector) and methyl methacrylate by GC-FID (gas chromatography-flame ionization detector). The migration level of monomers were within the migration limits of Ministry of Food and Drug Safety (MFDS). As a result of safety evaluation, our results showed that the estimated daily intake (EDI, mg/kg bw/day)s were $2.39{\times}10^{-9}$ and $1.20{\times}10^{-9}$ for 4,4'-MDA and 2,4-TDA of PA, $4.32{\times}10^{-9}$ for acrylonitrile of ABS and $2.27{\times}10^{-7}$ for methylmethacrylate of acrylic resin. Reference Dose (RfD, mg/kg bw/day) of acrylonitrile and tolerable daily intake (TDI, mg/kg bw/day) of methacrylate were established respectively as 0.001 by EPA (US Environmental Protection Agency) and as 1.2 by WHO (World Health Organization). When comparing with RfD and TDI, the EDIs of acrylonitrile and methylmethacrylate accounted for $4.32{\times}10^{-4}%$ and $1.89{\times}10^{-5}%$ respectively.