• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.621-625
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• 1993

Kinetic studies are conducted for the reactions of Y-benzoyl, Y-benzenesulfonyl and Y-benzyl halides with X-anilines in acetonitrile, and the transition state (TS) structures and their variations with substituents X and Y are discussed. The magnitude of the cross-interaction constants, $\rho$xy, is the largest and the inverse secondary kinetic isotope effect (SKIE), $k_H/k_D$ < 1.0, with deuterated aniline nucleophiles is the smallest for benzoyl fluoride reflecting the tightest TS for this compound. The SKIEs for sulfonyl halides are relatively large due to a relatively large, diffuse nature of the reaction center, S, causing weaker steric hindrance to the vibrations of the two N-H(D) bonds. For benzoyl and sulfonyl halides, the trends in $k_H/k_D$ and $Ir_XI$ variations with $\sigma$Y contradict each other, which is rationalized by the negative charge accumulation on the reaction center, CO and SO$_2$, causing inefficient transfer for the substrate with an electron donating substituent.

• Journal of The Korean Society of Grassland and Forage Science
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• v.27 no.3
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• pp.167-172
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• 2007

Manure recycle is an emerging issue in agriculture in Korea these days. Farmers are keeping eye on legume mixture with grasses for nitrogen fixation and transfer to companion crops by legumes. We had a trial to investigate the effect of different legume mixtures on nitrogen fixation and transfer in spring soil. The treatment was arranged in a randomized complete block design with three replications. Three different mixtures were used(rye+hairy vetch, Italian ryegrass+crimson clover, oat+pea) and sowed in pots with paddy soil from western part of Korea(Seo Chon County). Pots with rye+vetch were transplanted from field of RDA(rural development administration) in Suwon on 2 February 2007 and other mixture treatments were sowed on early March with different sowing rate(7:3=Italian:crimson, 6:4=oat:pea). $(^{15}NH_4)_2SO_4$ solution at. $99.8\;atom%^{15}N$ was applied to the each pot at the rate of $2kg\;N\;ha^{-1}$. Application was done on 6 April at rye+vetch pots and remainder were applied on April 16. Forage were harvested from each pot at ground level in heading stage and separated into legume and grass. Total N content and $^{15}N$ value were determined using a continuous flow stable isotope ratio mass spectrometry. DM yield of rye+vetch, Italian+crimson and oat+pea were 6,607, 3,213 and 4,312 kg/ha, respectively. Proportion of N from fixation was 0.73(rye+vetch), 0.42(Italian+crimson) and 0.93(oat+pea). The percentages of N transfer from legume to grass were from 61% to 24% in different method by treatment and -35% to 21% in isotope dilution method.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.5
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• pp.282-287
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• 2017

The purpose of this study was predicted the effects of mixing and diffusion due to the operation of the apparatus before the development of the mixed diffusion device for the decontamination absorbent to minimize the influence of contaminant inflow due to radiation accident. The tracer used for the flow characteristics was $^{68}Ga$, $^{99m}Tc$, which is a radioactive isotope, and 2 inch NaI radiation detector was used to detect it. The impeller of the decontamination mixed diffusion system applied to this study was made into three types and the mixing diffusion effect was compared. As a result of analyzing the flow characteristics of the radio-isotope with decontamination mixed diffusion device, mixing, diffusion and flow pattern were obtained. The radial mixing type impeller was able to diffuse to the water surface by the upflow flow, and the fin structure was adjusted for finding optimal conditions. The model 3 type consists of a fin guiding part and an auxiliary fin so that the diffusion speed is higher than that of other types of impellers. It also showed a short time to reach complete mixing.

• Ocean and Polar Research
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• v.30 no.3
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• pp.303-312
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• 2008

Despite the impacts of the climate changes on the pelagic ecosystem, few studies have examined the pelagic-benthic coupling in the adjacent East China Sea and Korea Strait. Therefore, the species composition and abundance of the macrobenthic community, as well as the potential food sources of benthic fauna were investigated in the present study using stable isotope analysis (${\delta}^{13}C\;and\;{\delta}^{15}N$) for suspended particulate organic matter (SPOM), sedimentary organic matter (SOM), phytoplankton, and zooplankton. A total of 157 macrobenthic fauna were collected, and the density of the macrobenthic fauna ranged from 4 to 434 ind./0.25 $m^2$, with an average density of 149 ind./0.25 $m^2$. The density of the benthic fauna increased moving from offshore shelf sites to coastal sites adjacent to the Korea Strait. Cluster analysis showed that the macrobenthic communities consisted of three distinct groups: group A in the Korea Strait, group B in the East China Sea, and group C near Ieodo. The dominant species in group A were the amphipods Photis japonica and Ampelisca miharaensis, followed by the polychaete Scolotoma longifolia. Environmental variables, such as the temperature of the seawater and sediment, and oxygen, and chlorophyll a levels, appeared to affect the structure of the community, suggesting the importance of coupling with the pelagic system. The ${\delta}^{13}C$ values of SPOM and zooplankton ranged from -22.97 to -23.5% and -19.92 to -21.86%, respectively, showing a relatively narrow range(<1%) between the two components. The difference between the ${\delta}^{13}C$ values of SOM and pelagic organic matter was also within 1%, suggesting that the SOM originated from the pelagic system, which is an important factor controlling the macrobenthic community.

• Asian-Australasian Journal of Animal Sciences
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• v.20 no.4
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• pp.536-542
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• 2007

The responses of whole body protein and glucose kinetics and of nitrogen (N) metabolism to non-protein energy intake (NPEI) were determined using an isotope dilution approach and measurement of N balance in three adult male goats. The diets containing 1.0, 1.5 and 2.0 times ME maintenance requirement, with fixed intake of CP (1.5 times maintenance) and percentage of hay (33%), were fed twice daily for each 21 d experimental period. After an adaptation period of 11 d, N balance was determined over 3 d. On day 17, whole body protein synthesis (WBPS) and glucose irreversible loss rate (ILR) were determined during the absorptive state by a primed-continuous infusion of [$^2H_5$]phenylalanine, [$^2H_2$]tyrosine, [$^2H_4$]tyrosine and [$^{13}C_6$]glucose, with simultaneous measurements of plasma concentrations of metabolites and insulin. Ruminal characteristics were also measured at 6 h after feeding over 3 d. Nitrogen retention tended to increase (p<0.10) with increasing NPEI, although digestible N decreased linearly (p<0.05). Increasing NPEI decreased (p<0.01) ammonia N concentration, but increased acetate (p<0.05) and propionate (p<0.05) concentrations in the rumen. Despite decreased plasma urea N concentration (p<0.01), increased plasma tyrosine concentration (p<0.05), and trends toward increased plasma total amino N (p<0.10) and phenylalanine concentrations (p<0.10) were found in response to increasing NPEI. Increasing NPEI increased ILR of both glucose (p<0.01) and phenylalanine (p<0.05), but did not affect ($p{\geq}0.10$) that of tyrosine. Whole body protein synthesis increased (p<0.05) in response to increasing NPEI, resulting from increased utilization rate for protein synthesis (p<0.05) and unchanged hydroxylation rate of phenylalanine ($p{\geq}0.10$). These results suggest that increasing NPEI may enhance WBPS and glucose turnover at the absorptive state and improve the efficiency of digestible N retention in goats, with possibly decreased ammonia and increased amino acid absorption. In addition, simultaneous increases in WBPS and glucose ILR suggest stimulatory effect of glucose availability on WBPS, especially when sufficient amino acid is supplied.

• Economic and Environmental Geology
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• v.24 no.2
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• pp.97-105
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• 1991

Oxygen and sulfur isotope composition of pyrophyllite and pyrite from six pyrophyllite deposits in the Yangsan-Milyang areas (the Cheonbulsan, Dumyong, Dongrae, Youkwang, Sungjin and Milyang mines), and five deposits in the Whasoon-Dado-Haenam areas (the Byuksong, Songseok, Dado, Bugock and Nowha mines) were measured. Pyrophyllite ores both from the Yangsan-Milyang areas and the Dado-Haenam areas are composed mainly of high alumina minerals such as pyrophyllite, sericite and kaolinite. Most of altered rocks show diagnostic chacteristics of bleaching effect. Major minerals of the Songseok ore deposit in the Whasoon area are pyrophyllite, and diaspore with minor amounts of kaolinite and quartz. The Byuksong ores from the Whasoon area were composed mainly of andalusite, kaolinite, pyrophyllite and mica with small amounts of chloritoid, quartz and carbonaceous matter. The Byuksong and Songseok ores show metamorphic textures such as porphyroblastic, and pressure solution textures, and have low whiteness values, The ${\delta}^{18}O$ values of pyrophyllite from the Cheonbulsan and Dumyong mines in the Yangsan area, and the Dado and Nowha mines in the Dado-Haenam areas were in the range of 0.23~5.36%,. The relatively low 8 180 values provide conclusive evidence for hydrothermal activity in these deposits. The ${\delta}^{18}O$ values of pvrophvllite from the Songseok mine in the Whasoon area were measured as 6.70-8.13%, and these higher ${\delta}^{18}O$ values suggest that the Songseok ore deposit have been probably subjected to metamorphism. ${\delta}^{34}$S(pyrito) values from the Cheonbulsan, Dumyong, Youkwang, Dongrae, Sungjin and Milyang deposits in the Yangsan-Milyang areas, and the Dado pyrophyllite deposits in the Dado area range from -5.8 to 2.7%, which means that the pyrite sulfur could be of igneous origin. ${\delta}^{34}$S(pyrito) from the Nohwa mine in the Haenam area is, however, measured as -12.4%" implying the contamination of sulfur derived from the sedimentary country rocks. All of the studied high alumina deposits in the Yangsan-Milyang areas and the Dado-Haenam areas were hydrothermal in origin, whereas the Byuksong and Songseok ore deposits in the Whasoon area were probably of metamorphic origin.

• Nuclear Engineering and Technology
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• v.13 no.3
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• pp.145-152
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• 1981

Even though a lately reported method of high temperature exchange labelling of o-iodo-hippuric acid (Hippuran) in the absence of oxidizing agent was considered to be an attractive one, the exchange mechanism was somewhat unclear. In this study iodine isotope exchanges between o-iodohippuric acid (OIH) and radioiodide ($^{125}$ $I^{ }$) or between OIH and molecular radioiodine ($^{125}$ $I_2$) were carried out at two different temperatures. Rate constants and activation parameters were measured by applying a radio-paper chromatography technique. Since o-iodobenzoic acid is known as a by-product in the exchange labelling of OIH, data were also obtained for the OIB-iodide systems for comparison. The rate constant was increased in the order of OIB...$^{125}$ $I^{[-10]}$ >OIB...$^{125}$ $I_2$>OIH..$^{125}$ $I^{[-10]}$ >OIH...$^{125}$ $I_2$ and the activation parameters for OIH were generally larger than those for OIB :$\Delta$H$\neq$$_{OIH}$>$\Delta$H$\neq$$_{OIB}$, $\Delta$S$\neq$$_{OIH}$>$\Delta$S$\neq$$_{OIB}$. These results suggest that the mechanism of the high temperature exchange is predominantly nucleophilic even though some electrophilic character can also be involved depending upon reaction conditions. Such a fact may well be caused by a feasible formation of hydrogen bonding type transition state due probably to the ortho substituent effect of-CONHC $H_2$COOH. Thus, the high temperature exchange method is estimated to be quite effective for labelling Hippuran especially at a small research center where reducing agent-free $^{131}$ I is unavailable.ailable..

• Analytical Science and Technology
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• v.37 no.3
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• pp.166-173
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• 2024

Steroids have a temporary skin improvement and whitening effect by controlling vasodilation, but they also cause side effects when used for a long time. Therefore, steroids were designated and managed as raw materials that cannot be used in cosmetics in Korea. However, steroids are continuously being detected in cosmetics, causing social issues. In this study, we developed a certified reference material (CRM) for the determination of steroids such as hydrocortisone in cosmetics. A cream-type cosmetic CRM was manufactured and subsequently certified following the guidelines outlined in ISO Guide 35. Homogeneity, short-term stability, and long-term stability were evaluated using isotope dilution mass spectrometry (ID-MS). The certified values were determined by using NIST's primary reference material to ensure traceability. From now on, we intend to supply the certified reference material as a cosmetic CRM to national and international companies, as well as research institutes after certification as certified reference material from KOLAS and registering on COMAR.