• Korean Chemical Engineering Research
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• v.53 no.1
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• pp.53-56
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• 2015

In this study, investigated the synthesis method of p-Phenylenediamine (PPD) by amination of p-Diiodobenzene (PDIB) under supercritical ammonia and CuI catalyst conditions. We examined the effects of various process variables (e.g., reaction temperature, pressure, amount of ammonia inserted, amount of catalyst inserted, and reaction time) on the production yield of PPD by analyzing the Gas Chromatography (GC). The experimental results demonstrated that PPD was not produced under non-catalyst conditions, and PPD production yield increased with increasing temperature, pressure, amount of catalyst inserted, and reaction time. However, for the reaction temperature case, it was found that $200^{\circ}C$ was the optimal temperature, because thermal degradation of PPD occurred above $250^{\circ}C$. In addition, we confirmed the structure of PPD and the bonding characteristics of the amine group via FT-IR and H-NMR analysis.

• Journal of the Korean Society of Food Science and Nutrition
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• v.34 no.9
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• pp.1330-1335
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• 2005

Red brownish p-pheylenediamine (PPD) has been widely used hair dye for women. The dye was known to cause systemic anaphylaxis, dermatitis and bladder cancer. But the effect of PPD toxicity with oxygen free radical has not been studied. This study investigated the degree of skin injury by PPD. PPD ($2.5\%$ PPD in $2\%\;NH_{4}OH$) was applied to the rat skin ($25 mg/16.5\;cm^2$) 3 or 5 times every other day. Histopathological findings demonstrated the proliferation of epithelial cells and the increased keratinization by PPD. The activities of glucose 6-phosphatase (G6Pase) was decreased and acid phosphatase (ACP) was increased in PPD-applied rat skin. Groups in which PPD was applied 5 times were more damaged than groups applied 3 times. To examine the relationship between tissue damage and oxygen free radicals, effect of PPD on xanthine oxidase (XO) activity was measured and XO activity was more significantly increased in the group treated with PPD 5 times than 3 times. However, reduced glutathione (GSH) content, and the activities of catalase (CAT), super-oxide dismutase (SOD) and glutathione S -transferase (GST) were more decreased in PPD-applied groups than in controls. Even though the activities of XOD was not changed in the group treated with PPD 3 times, the decreased activities of oxygen free radical system and the damaged skin tissue were observed. This result might be caused by the production of toxic PPD metabolites in rat skin. In conclusion, topical PPD application led to skin injury in a dose-dependent manner, probably due to the generation rate of oxygen free radical.

• Biomedical Science Letters
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• v.9 no.2
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• pp.75-84
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• 2003

To evaluate the influence of hepatic oxygen free radical systems on liver injury by topical p-phenylenediamine (PPD) application on rat skin, PPD (25 mg/16.5 $\textrm{cm}^2$) was topically applied to the abdominal region 5 times every other day and sacrificed. By PPD treatment, increasing rate of liver weight/body weight (%), serum activities of alanine aminotransferase and aspartate aminotransferase and decreasing rate of microsomal glucose-6-phosphatase activity were higher in the rats fed tungstate supplemented diet than those fed a standard diet. These findings indicate that group fed tungstate supplemented diet have more severe liver injury compared with group fed standard diet on topical PPD application. However, the activities of oxygen free radical generating enzymes such as xanthine oxidase (XO) and cytochrome P450 dependent aniline hydroxylase and those of oxygen free radical scavenging enzymes were not found to be different between these two animal groups. In the present study, a novel monitoring method to detect the generating of oxygen free radicals in liver extract was devised. Throughout this method, the oxidized PPD produced by oxygen free radicals was determined colorimetrically. The increasing rate of PPD oxidation by liver homogenate was higher in tungstate fed animals than in standard diet fed ones. Among the fractionations of liver extract, the mitochondrial and postmitochondrial fractions in the liver extract of tungstate fed animals led to a higher availability of PPD oxidation by PPD treatment compared with standard diet fed ones. In conclusion, these results suggest that an enhanced liver injury in tungstate fed animals treated with PPD may be due to oxygen free radicals produced in other systems except oxygen free radicals generating from cytosolic XO system. Especially, oxidative availability by PPD can be used for oxygen free radical detection in some tissue.

• Journal of the Korean Society of Food Science and Nutrition
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• v.35 no.8
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• pp.1010-1015
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• 2006

p-Pheylenediamimine (PPD) is one of hair dye's ingredients, and the mixture of PPD with hydrogen peroxide is generally used to dye hair at beauty shop. This study is conducted to investigate the effect of oxidized PPD on rat skin. 6% hydrogen peroxide, PPD (5% PPD in 2% $NH_4OH$) or the mixture (isovolumed mixture of 5% PPD and 6% hydrogen peroxide in 2% $NH_4OH$) was applied to rat skin ($25\;mg/16.5\;cm^2$) five times every other day. The activity of acid phosphatase (ACP) was more increased in the mixture of PPD with hydrogen peroxide applied group than PPD applied group. Furthermore, the activity of glucose 6-phosphatase (G6Pase) in the mixture of PPD with hydrogen peroxide applied group showed higher decreasing rate than that of PPD applied group. In histopathological findings, the mixed PPD with hydrogen peroxide applied group showed more thickening of epithelium, increased numbers of dermal fibroblasts, and the dilatation of dermal capillaries than PPD applied group. The significant increasing of xanthine oxidase (XO) activity was determined in mixture of PPD with hydrogen peroxide applied group compared with PPD applied group. However, reactive oxygen species (ROS) scavenging system, the activities of superoxide dismutase (SOD) and glutathione S-transferase (GST) were more significantly decreased in mixed PPD with hydrogen peroxide applied groups than in PPD applied group. In conclusion, topical application with the mixture of PPD with hydrogen peroxide compared with PPD application resulted in imbalance with ROS generating and scavenging which probably led to severe skin injury.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.425-430
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• 2016

p-Phenylenediamine (PPD) was synthesized by aromatic amination of p-diiodobenzene (PDIB) using liquid ammonia and Cu-catalysts. The effects of the catalyst, reductant, ammonia quantity and reaction temperature on PPD production were investigated. Cu(I) compounds and Cu powder were selected as catalyst due to a higher selectivity than Cu(II) compounds. As the catalyst quantity increased, rate of PPD production as well as side reaction of aniline decreased with increasing the quantity of ammonia. Reductants such as ascorbic acid, hydrazine and dihydroxyfumaric acid were tested to lower the catalyst loading. The use of reductants resulted in increasing the reaction rate but also increased the amount of aniline The rate of reaction using ascorbic acid or dihydroxyfumaric acid was faster than that using hydrazine. The lowest side reaction of aniline was found in dihydroxyfumaric acid of reductants investigated.

• Applied Chemistry for Engineering
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• v.10 no.8
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• pp.1210-1215
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• 1999

Optimum conditions of the hydrogenation of PNA to pure PPD were determined in a three-phase slurry reactor with suspended Pd/C catalyst particles. Minimization of mass transfer resistances at the interfaces of both gas-liquid and liquid-catalyst particles and control of overall reaction rate on catalyst surface leaded to decrease the hydrogen starvation on reaction active sites and to reduce the side reactions during hydrogenation. The optimum temperature, pressure, and catalysst concentration were confirmed to be in the range of $60^{\circ}C$, 60~70 psig, and 1~2 g-cat/L, respectively. Reaction rate was zero order with respect to the concentration of PNA and 1st order with respect to the pressure of hydrogen(P). Overall rate expression of the reaction was $R_A=6.44{\times}10^6{\cdot}H{\cdot}P{\cdot}m{\cdot}$exp(-4659/T) where H is constant, m is concentration of catalyst, and T is temperature.

• Bulletin of the Korean Chemical Society
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• v.25 no.8
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• pp.1195-1201
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• 2004

Tyrosinase was covalently immobilized on platinum electrode according to the method we developed for laccase (Bull. Korean Chem. Soc. 2002, 23(7), 385) and p-chlorophenol, p-cresol, and phenol could be detected with sensitivities of 334, 139 and 122 nA/ ${\mu}M$ and the detection limits of 1.0, 2.0, and 2.5 ${\mu}M$, respectively. The response time ($t_{90\%}$) is 3 seconds for p-chlorophenol, and 5 seconds for p-cresol and phenol. The optimal pHs of the sensor are in the range of 5.0- 6.0. This sensor can tolerate at least 500 times repeated injections of p-chlorophenol with retaining 80% of initial activity. In case of tyrosinase and laccase co immobilized platinum electrode, the sensitivities are 560 nA/ ${\mu}M$ for p-phenylenediamine (PPD) and 195 nA/ ${\mu}M$ for p-chlorophenol, respectively. The sensitivity of the bi-enzyme sensor for PPD increases 70% compared to that of only laccase immobilized one, but the sensitivity for p-chlorophenol decreases 40% compared to that of only tyrosinase immobilized one. The sensitivity increase for the bi-enzyme sensor for PPD can be ascribed to the additional catalytic function of the co-immobilized tyrosinase. The sensitivity decrease for p-chlorophenol can be explained by the “blocking effect” of the co-immobilized laccase, which hinders the mass transport through the immobilized layer. If PPD was detected with the electrode that had been used for p-chlorophenol, the sensitivity decreased 20% compared to that of the electrode that had been used only for PPD. Similarly, if p-chlorophenol was detected with PPD detected electrode, the sensitivity also decreased 20%. The substrate-induced conformation changes of the enzymes in a confined layer may be responsible for the phenomena.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.377-380
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• 2015

In this paper, we have investigated the optimization of $I_2$ recovery process from $NH_4I$ solution, which is generated as by-product during the amination reaction of p-diiodobenzene (PDIB) for p-phenylenediamine (PPD) synthesis. The recovered $I_2$ is then recycled as a raw material for PDIB synthesis. We have employed a cation exchange resin to recover $I_2$ from $NH_4I$ sample solution, and determined the breakthrough point and exchange capacity from the breakthrough curve. Furthermore, we have suggested optimum conditions of our $I_2$ recovery process by measuring the purity and yield of recovered $I_2$ with respect to the concentrations of $NH_4I$ and oxidant ($H_2O_2$) solutions, the oxidation time, and the temperature of drying process. Finally, the yield and purity as high as 94.96% and 96.65%, respectively were obtained by reusing the residual solution still containing unrecovered iodide ions.

• Journal of the Korean Chemical Society
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• v.18 no.5
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• pp.381-388
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• 1974

When mixture of p-phenylenediamine (PPD) and m-aminophenol (MAP) were reacted with formaldehyde (F) varying their amounts under $N_2$ stream at the temperature of -5∼0$^{\circ}$, addition condensation reaction occurred and brown colored resins(in some cases orange colored) were formed immediately. All resins thus formed were insoluble in most ordinary organic solvents and did not melt up to 300$^{\circ}$. When the resins were treated with dilute(7 %) aqueous sodium hydroxide solution, the adsorptivity of methylene blue on them showed marked improvement reaching as much as 80 mg of methylene blue on 1 g of the resin. On the other hand, in the case of bromophenol blue, its amount of adsorption appeared 250 mg per 1 g of the resin. The TGA under $N_2$ atmosphere indicated that the resin formed in molar ratio of 1 : 3 : 8 (PPD : MAP : F) showed the best heat-resistant property among others. About 40 % weight loss was observed for this resin at 900$^{\circ}$ with heating rate of 2$^{\circ}$ per minute.

• Bulletin of the Korean Chemical Society
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• v.23 no.3
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• pp.385-390
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• 2002

Laccase could be successfully assembled on an amine-derivatized platinum electrode by glutaraldehyde coupling. The enzyme layer formed on the surface does not communicate electron directly with the electrode, but the enzymatic activity of the surf ace could be followed by electrochemical detection of enzymatically oxidized products. The well-known laccase substrates, ABTS (2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)) and PPD (p-phenylenediamine) were used. ABTS can be detected down to 0.5 ${\mu}M$ with linear response up to 15 ${\mu}M$ and current sensitivity of 75 nA/ ${\mu}M.$ PPD showed better response with detection limit of 0.05 ${\mu}M$, linear response up to 20 ${\mu}M$, and current sensitivity of 340 nA/ ${\mu}M$ with the same electrode. The sensor responses fit well to the Michaelis-Menten equation and apparent $K_M$ values are 0.16 mM for ABTS and 0.055 mM for PPD, which show the enzymatic reaction is the rate-determining step. The laccase electrode we developed is very stable and more than 80% of initial activity was still maintained after 2 months of uses.