• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.881-888
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• 1994

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.382-388
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• 1989

The approximate rates and stoichiometry of the reaction of excess potassium tri-sec-butylborohydride ($K_s-Bu_3BH$) with selected organic compounds containing representative functional groups were determined under the standard conditions (0$^{\circ}C$, THF) in order to define the characteristics of the reagent for selective reductions. Primary alcohols evolve hydrogen in 1 h, but secondary and tertiary alcohols and amines are inert to this reagent. On the other hand, phenols and thiols evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to the corresponding alcohols. Reduction of norcamphor gives 99.3% endo- and 0.7% exo-isomer of norboneols. The reagent rapidly reduces cinnamaldehyde to the cinamyl alcohol stage and shows no further uptake of hydride. p-Benzoquinone takes up one hydride rapidly with 0.32 equiv hydrogen evolution and anthraquinone is cleanly reduced to the 9,10-dihydoxyanthracene stage. Carboxylic acids liberate hydrogen rapidly and quantitatively, however further reduction does not occur. Anhydrides utilize 2 equiv of hydride and acyl chlorides are reduced to the corresponding alcohols rapidly. Lactones are reduced to the diol stage rapidly, whereas esters are reduced moderately (3-6 h). Terminal epoxides are rapidly reduced to the more substituted alcohols, but internal epoxides are reduced slowly. Primary and tertiary amides are inert to this reagent and nitriles are reduced very slowly. 1-Nitropropane evolves hydrogen rapidly without reduction and nitrobenzene is reduced to the azoxybenzene stage, whereas azobenzene and azoxybenzene are inert. Cyclohexanone oxime evolves hydrogen without reduction. Phenyl isocyanate utilizes 1 equiv of hydride to proceed to formanilide stage. Pyridine and quinoline are reduced slowly, however pyridine N-oxide takes up 1.5 equiv of hydride in 1 hr. Disulfides are rapidly reduced to the thiol stage, whereas sulfide, sulfoxide, sulfonic acid and sulfone are practically inert to this reagent. Primary alkyl bromide and iodide are reduced rapidly, but primary alkyl chloride, cyclohexyl bromide and cyclohexyl tosylate are reduced slowly.

• Journal of Korean Society of Transportation
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• v.8 no.2
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• pp.119-131
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• 1990

Physico-chemical properties of asphalt, aggregate, and asphalt-aggregate mixture that might influence stripping were summarized in Table 1, based on the fundamental theories concerning stripping. It was found that although physical properties of aggregate affected stripping, there was no strong correlation between the physical properties of aggregate, such as pore volume and surface area, and the stripping propensity of the aggregate. Chemical and electrochemical properties of aggregate surface in the presence of water were most important factors for stripping. All mineral aggregates tested in this study imparted distinctive pH values to the contacting water and possessed distinctive electrochemical properties as measured by zeta potential. It was found that aggregates which had relatively higher surface potential in water and/or which imparted relatively higher pH to the contacting water were more susceptible to stripping. The functionalities contained in antistripping additives tested were primary and secondary amines and those of organic nitrogen compounds. The functionalities were determined by examining their infrared spectra. Based on the interfacial energy concept, the contact angle of an asphalt drop on an aggregate surface immersed in water related to the stripping propensity. The contact angle and stripping propensity were markedly reduced by the presence of an antistripping additive. In general, all the additives tested improved stripping resistance to some extent, depending on their concentration in the asphalts. The optimum dosage of an additive varied with different asphalts, as well as different aggregates. All antistripping additives tested in this study lost their effectiveness and failed to function to some extent when maintained for hours in a hot asphalt.

• Journal of the Korean Society of Food Science and Nutrition
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• v.43 no.8
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• pp.1207-1216
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• 2014

Vegetables contain high levels of nitrate, which can be converted to nitrite for reaction with secondary amines to form nitrosamines. In this study, we evaluated safety effects against nitrite and nitrosamine as well as anti-mutagenic activities of vegetable juices. To do this, the contents of nitrate, nitrite, and nitrosamines were determined in vegetable juices. The safety effects against nitrite and nitrosamine formation were also investigated under simulated human gastric conditions. The contents of nitrate and nitrite in common and organic kale and Angelica keiskei juices were 931~2,052 mg/kg and 13~82 mg/kg, respectively. However, seven kinds of nitrosamines were not detected in the vegetables juices. The nitrate content decreased when vegetable juices were digested under simulated human gastric conditions. Nitrosamine (N-nitrosodimethylamine) formation under simulated human gastric conditions was inhibited by addition of vegetable juices. In addition, vegetable juices, especially organically cultivated juices, showed anti-mutagenic effects in a Salmonella assay system. These results suggest that organically cultivated vegetable juices are a promising health-promoting source.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3588-3592
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.15 no.2
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• pp.147-153
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• 1982

Nitrate and nitrite, which readily produce N-nitrosamines by reaction with secondary amines, are widely distributed in natural products such as vegetables and cereals, and are also used as a color fixation in meat products or fish roes. This experiment was carried out to determine the contents of nitrate and nitrite in foods such as fermented sea foods and fresh vegetables purchased at markets in Korea. The contents of nitrate were $0.74\sim13.81\;ppm$ for fermented sea foods and $4.0\sim1,572.5\;ppm$for fresh vegetables. As for vegetables, the nitrate levels of edible herbs were relatively higher than those of greens, fruits and rootcrops. The nitrite contents in fermented demoisells(Chromis notatus), fermented shrimp, fermented small squid, fermented anchovy and salted Alaska pollack roe were very little, while those in fermented hairtail and fermented entrails were not detected. As for vegetables, nitrite levels found for cabbage and lettuce were relatively as high as 3.8 ppm and $2.5\sim2.9\;ppm$, respectively, but were not detected in Korean cabbage, green perilla leaf, pepper, garlic and burdock. Of vegetables, the nitrate values in the outer part of Korean cabbage, stems of water cress and leaves of green onion were higher than in the other parts. Little variety of the nitrate levels were found during 4 days storage. In the comparison of low temperature storage and room temperature storage, lettuce, pumpkin and spinach contained higher levels of nitrate at low temperature storage, while eggplant and green onion, at room temperature storage.

• Journal of Food Hygiene and Safety
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• v.33 no.5
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• pp.361-368
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• 2018

N-nitrosamines are probable or possible human carcinogens, which are produced by the reaction between secondary amines and nitrogen oxide in the acidic environment or by heating. Common risk assessment procedure involves the comparison between exposures expressed in the unit, mg/kg body weight/day and the Health-Based Reference dose expressed in the same unit. This procedure is suitable for the policy decision-making and is considered as inappropriate for the consumers to get information about their dietary decision-making. Therefore, the distributions of NDMA (N-nitrosodimethylamine), NDBA (N-nitrosodibutylamine), the six N-nitrosamines (NDMA, NDBA, NDEA (N-nitrosodiethylamine), NPYR (N-nitrosopyrrolidine), NPIP (N-nitrosopiperidine), and NMOR (N-nitrosomorpholine) in the menus grouped based on the presence of main ingredients and cooking methods were analyzed to generate consumer-friendly information regarding food contaminants. Recipes and intakes were taken from 2014 to 2016 KNHANES (The Korean National Health and Nutrition Examination Survey) and only the data from ages of 7 years or older were used. The contamination data were collected from the 2014~2016 Total Diet Study and all the analysis were performed using R software. Rockfish, eel, anchovy broth and pollock were mainly exposed to N-nitrosamines. In terms of cooking methods, soups and stews appeared to contain the highest amount of N-nitrosamines. Cereals, fruits, and dairy products in the ingredient categories, and rice dishes and rice combined with others in recipe categories had the lowest level exposure to N-nitrosamines. In case of N-nitrosamines, unlike other cooking related food contaminants, boiled dishes such as soups and stews and dishes mainly consisting of fishes and shellfishes had highest level of exposure, showing a large discrepancy with the previous thought of processed meat is the main source of N-nitrosamines.