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Molecular Orbital Studies on the Reaction Path and Reactivity of $S_N2$ Reactions. Determination of Reactivity by MO Theory (Part 69) (SN2 반응의 반응경로 및 반응성에 관한 분자궤도함수 이론적 연구)

  • Lee, Ik Choon;Cho, Jeoung Ki;Lee, Hae Hwang;O, Hyeok Geun
    • Journal of the Korean Chemical Society
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    • v.34 no.3
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    • pp.239-247
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    • 1990
  • The gas-phase S_N2$ reactions can be classified into neutral bimolecular, solvated, and ionic reactions; the neutral bimolecular reaction proceeds via retention mechanism whereas the ionic reaction produces inversion products. In the reaction of solvated nucleophile with one solvent molecule, a six-center transition state (TS) is formed and the two processes i.e., retention and inversion, are found to compete with a favored path depending on the electronic effect of the nucleophile and substituents in the substrate and on the steric requirement. In the ionic reaction, the difference in the energy barrier between the two processes reduces to a small value when the substrate methyl group is made bulky, leaving ability of the leaving group is improved and at the same time the negative charge of the nucleophile is dispersed. When the reaction center atom in the $S_N2$ reaction is changed to a larger sized second row elements, the activation barrier decreases since the steric crowding in the penta-coordinated TS is relieved. However within the same row, the barrier was found to increase as the atomic size decreased. For the boron, B, the barrier height was the least since in addition to the relatively large atomic size compared to C and N, it forms tetra-coordinated TS so that the steric crowding becomes nearly negligible.

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An Analysis of STS Materials in Chemistry Parts of Middle School Science Textbooks (제 6차 교육과정에 따른 중학교 과학 교과서(화학단원)의 STS 내용 분석)

  • Kim, Yun Hi;Kwon, Hyo Jin;Moon, Seong Bae
    • Journal of the Korean Chemical Society
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    • v.43 no.3
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    • pp.321-327
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    • 1999
  • The STS materials, emphasized in the 6th curriculum, in the chemistry part of middle school science textbooks were analyzed. The average value of the STS content of textbook was 13.2%. In the study of chapter of textbook, 15.9% of STS materials was included in the chapter of ?reaction of materials?, 12% in "character and separation of materials", and 10.8% in "composition of materials". When the STS topics classified by Piel were analyzed, the results were as follows; 40.2% on sociology of science, 28.8% on environmental quality and utilization of natural source, 20.4% on effects of technological developments, and 12.9% on energy. However, the topic on human engineering was only included in a textbook, and the topics on space research and national defence were not included in any textbooks. When the STS materials were analyzed by student activities of SATIS, the number of activities was 71. Most activities were consisted of solving problems and decision, simulation and data analysis, and there was no research design and role playing.

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Effects of Temperature and n-Alcohols (Propanol, Butanol, Pentanol and Hexanol) on the Micellization of Cetyltrimethylammonium Bromide (Cetyltrimethylammonium Bromide의 미셀화 현상에 미치는 온도 효과 및 n-알코올(프로판올, 부탄올, 펜탄올 및 헥산올) 효과)

  • Lee, Byeong Hwan
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.539-546
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    • 1994
  • The critical micelle concentration(CMC) and the counterion binding $constant(\beta)$ at the CMC of cetyltrimethylammonium bromide(CTAB) in a series of aqueous solutions containing medium chain-length n-alcohols(Propanol, Butanol, Pentanol and Hexanol) have been determined from the concentration dependence of electrical conductance at serveral temperature from $17^{\circ}C\;to\;41^{\circ}C.$ Thermodynamic parameters $({\Delta}G^o_m,\;{\Delta}H^o_m,\;{\Delta}S^o_m,\;and\;{\Delta}C_p)$ associated with micelle formation of CTAB have been also estimated from the temperature dependence of CMC and $\beta$ values, and the significance of these parameters and their relation to the theory of micelle formation have been considered. The results show that an enthalpy-entropy compensation effect is usually observed for the micellization of CTAB. The effects of n-alcohols on the micellar properties (CMC and $\beta$) of CTAB solutions have been also investigated. The addition of n-alcohol to the CTAB solution in a small quantity decreases the CMC value and the counterion binding constant $(\beta)$ at the CMC, but the addition of n-alcohol in an excessive quantity increases the CMC values on the conterary. These results have been explained in terms of the effect of the micelle-solubilized alcohol on the micellar surface charge density.

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Synthesis of New N2O Tridentate Ligands and Their Stability Constants of Transition Metal Complexes (새로운 N2O계 세 자리 리간드의 합성과 전이금속 착물 안정도상수)

  • Kim, Sun-Deuk;Park, Young-Sik
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.569-577
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    • 2003
  • Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.

Complexation of Cadmium(Ⅱ) with Soil Fulvic Acid : Effect of pH and Fulvic Acid Concentration (풀빅산과 카드뮴(Ⅱ)과의 착화합 반응 : 풀빅산의 농도와 pH의 영향)

  • Choe, Se Yeong;Jeong, Geun Ho;Jeon, Song Hui;Mun, Hui Jeong
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.585-589
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    • 1994
  • The complexation of cadmium(II) with a well characterized local soil fulvic acid was investigated at different solution pH and fulvic acid concentration using ion selective electrode. The stability constants were determined using a continuous distribution model based on Scatchard Plot; this model takes into consideration the diversitv of cation binding sites on a naturally occurring organic macromolecules even if the nature of the binding sites may not be known. The mean value of $logKi(\mu)$ was found to increase at higher pH(pH 4.0: ${\mu}=3.79{\pm}0.74$ l\;mol^{-1}; pH 6.0: ${\mu}=4.51{\pm}0.78$ l\;mol^{-1}$), and in more dilute fulvic acid concentration([FA] = 50 mgl$^{-1}: {\mu}=4.16{\pm}0.60$ l\;mol^{-1}; [FA]=151 mgl$^{-1}:{\mu}=3.75{\pm}0.5\;l\;mol^{-1}$). The intrinsic constant(logKint) for binding at the strongest site was measured to be around $4.72\;l\;mol^{-1}$ at both pH4.0 and 5.0, but was found to be increased to $6.03\;l\;mol^{-1}$ when pH was 6.0.

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Effect of Variable Feed Allowance with Constant Protein Input on Water Quality in Channel Catfish Production Ponds

  • Cho Sung Hwoan
    • Fisheries and Aquatic Sciences
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    • v.1 no.2
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    • pp.192-200
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    • 1998
  • This study was carried out to evaluate the effect of feeding higher protein feeds with lesser amount, but feeding the constant total protein input for all treatments, on water quality and nitrite toxicity in channel catfish ponds. There was no significant difference in survival rate among treatments $(P>0.05)$. Specific growth rate (SGR) for Treatment 1$(28\%\;protein\;and\;100\%\;of\;satiation)$ was significantly higher $(P>0.05)$ than for Treatment 3$(36\%\;protein\;and\;87.5\%\;of\;satiation)$, but not significantly higher than for Treatment 2 $(32\%\;protein\;and\;77.8\%\;of\;satiation)$ at constant digestible energy (DE), 3.08kcal/g (treatments 1, 2 and 3). At constant DE/P (treatments 4, 2 and 5), no significant difference in SGR was observed among treatments. Feed conversion ratio (FCR) slightly improved or improved as dietary protein level increased from $28\%$ to $32\%$ and feed allowance decreased by $12.5\%$, but did not improve as dietary protein level increased from $32\%$ to $36\%$ and feed allowance decreased by $22.2\%$, at constant DE and constant DE/P. There was no significant difference in water quality variables, such as total ammonia nitrogen (TAN), nitrite, chlorophyll a, soluble phosphorous concentrations among treatments, but significant difference in water quality variables over time as amount of feed fed increased $(P<0.0001)$. There was a trend toward increase in TAN and nitrite over time. A strong linear regression was observed between mean total ammonia nitrogen and nitrite for all treatments Y (Nitrite) =$0.04\times (TAN)+0.01$, $R_2=0.89$. Methemoglobin percent in the blood of catifish was not significantly different among treatments. And its mean value was $7.5\%$, which was relatively low, so that it was not serious problem in catfish production pond under these experiment conditions. There was the stronger linear regression between the percentage of Methemoglobin and the molar ratio of nitrite to chloride rather than nitrite alone: $Y\;(Methemoglobin\;\%)\;=\;58.45\;\times\;(NO^{2-}/Cl^-)\;+\;0.41,\;R^2=0.60$. These results indicate that deterioration of water quality has no strong impact on poor weight gain for $36\%$ dietary protein in this study.

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Isolation of Marine Bacteria Killing Red Tide Microalgae -III. Algicidal Effects of Marine Bacterium, Micrococcus sp. LG-5 against the Harmful Dinoflagellate, Cochlodinium polykrikoides- (적조생물 살조세균 탐색 -III. 유해성 적조생물 Cochlodinium polykrikoides에 대한 Micrococcus sp. LG-5의 살조 효과-)

  • JEONG Seong-Youn;PARK Young-Tae;LEE Won-Jae
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.33 no.4
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    • pp.331-338
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    • 2000
  • The algicidal effects of marine bacteria were investigated and a strain, which had the strongest algicidal activity against the harmful dinoflagellate, Cochiodinim polykrikoides was selected. The bacterium was isolated in seawater during the period of blooming of C. polykrikoides in Masan Bay. This algicidal bacterium was identified as Micrococcus sp. LG-5 by means of morphological and biochemical tests. The optimal culture conditions of Micrococcus sp, LG-5 were $25^{\circ}C,\;pH 7.0\;and\;3.0{\%}$ NaCl concentration. The algicidal activity of Micrococcus sp. LG-5 was significantly increased to maximum value in the late of logarithmic phase of cell cuture. In addition, the culture filtrate ($pore size,\;0.1{\mu}m$) of Microcoocus sp. LG-5 showed strong algicidal effects. The cell numbers of C. polykikoides were decreased from $1.2{\times}10^4 cells/ml\;to\;less\;than\;2{\times}10^3\;cells/ml$ within 3, 6, 30 hours at the concentrations of culture filtrate $10{\%},\;5{\%}\;and\;1{\%}$, respectively. These results indicated that the algicidal effect was mediated by certain substances released from Microooccus sp. LG-5.

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Utilization of Defatted Soybean Meal As a Substitute for Fish Meal in the Diet of Juvenile flounder (Paralichthys olivaceus) (넙치 치어 배합사료의 어분 대체 단백질원으로서 탈지 대두박 이용성)

  • KIM Yoon-Sook;KIM Bong-Seok;MOON Tae-Seok;LEE Sang-Min
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.33 no.5
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    • pp.469-474
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    • 2000
  • This study was conducted to investigate the utilization of defatted soybean meal as a substitute for fish meal in the diet for juvenile flounder (Paralichthys olivaceus). Duplicate groups of average weighing 35 g were fed one of four isonitrogenous ($54{\%}$) and isocaloric (575 kcal/100 g diet) diets containing $0{\%}, 10{\%}, 20{\%} and 30{\%}$ soybean meal for 45 days. Survival rates of all groups were $100{\%}$, Weight gain of fish decreased with increasing dietary soybean meal levels, However, this value was not significantly different between fish fed the control and $10{\%}$ soybean meal diet (P > 0.05). Feed efficiency and protein efficiency ratio decreased with increasing dietary soybean meal levels, but no significant differences were found among fish fed the control, $10{\%}\;and\;20{\%}$ soybean meal diets (P > 0.05). Daily feed and protein intake increased with increasing dietary soybean meal level. Crude protein and moisture content of liver tended to decrease and crude lipid content tended to increase with decreasing of dietary soybean meal levels. Plasma total cholesterol levels of fish fed the diets containing $20{\%}\;and\;30{\%}$ soybean meal were significantly lower than that of fish fed control diet (P < 0.05), Plasma GOT level significantly increased with increasing dietary soybean meal level (P < 0.05). It is concluded that soybean meal can be used as a partial substitute for fish meal up to $10{\%}$ in this dietary formulation for growth of juvenile flounder.

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A STUDY ON THE VICKER'S HARDNESS AND DIAMETRAL TENSILE STRENGTH OF HYBRID GLASS IONOMER (Hybrid Glass Ionomer cement의 비커스경도와 간접인장강도에 관한 연구)

  • Kwon, Kyun-Won;Park, Sang-Jin
    • Restorative Dentistry and Endodontics
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    • v.22 no.2
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    • pp.505-518
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    • 1997
  • The objective of this investigation was to compare the effects of water storage on the aspect of hardness and diametral tensile strengths of four hybrid glass ionomer cements(two compomers and two resin-reinforced glass ionomers) with a resin composite material. One composite resin(Degufill Ultra), two compomers(Dyract, Compoglass Cavifil), and two resin-reinforced glass ionomers(Fuji Duet, Vitremer) were used in this study. Cylindrical specimens were prepared and stored at $36{\pm}1^{\circ}C$ in distilled water for 10 minutes after set, and then tested on an Instron testing machine(No.4467) at 1.0 mm/min displacement rate. Vicker's hardness and diametral tensile strengths as time elapsed were measured after aging in water for 10 minutes, 1 hour, 3 hours, 1 day, 3 days, 5 days and 7 days at $36{\pm}1^{\circ}C$. During the test of diametral tensile strength, stress-strain curves were obtained, from which the compressive modulus were calculated and compared. The structure of four set glass ionomer cement mass was observed on SEM(Hitachi, S-2300) after being etched with 9.6% hydrofluoric acid for 1 minute. The results were as follows; 1. The hardness of the experimental group(compomer and the resin reinforced glass ionomer cement) did not exceed the value of control group(Degufill Ultra). 2. Vicker's hardness of the Fuji Duet tended to increase succeedingly, Dyract was decreased after 3 hours in water, and Vitremer was the lowest. 3. The control group(Degufill Ultra) presented progressively on increased diametral tensile strength with time, Fuji Duet were decreased after 3 days, Compoglass Cavifil and Vitremer were decreased after 5 days in water storage. 4. Compressive modulus of the control group(Degufill Ultra) and Dyract were increased sharply timely, Fuji Duet and Vitremer were increased smoothly by lapse of time in water. Fuji Duet were stronger than Vitremer. On the other hand, Vitremer exhibited the lowest toughness. 5. The microstructure of compomer was similar with that of the composite resin(Degufill Ultra), and the fillers in resin-reinforced glass ionomer cements were noticed. It can be concluded that mechanical properties of hybrid glass ionomer cements is weaker than composite resin, and that the compomers or the resin-reinforced glass ionomers can not substitute the composite resins. A plenty of considerations should be done on the application of them to the area under the loading and high wear has a little adverse effect on the mechanical properties on the water storage for 7 days. The further research should be needed to confirm the advantage of the compomer.

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A research on the medical theory of Choo-Joo(鄒澍) -- (추주(鄒澍)의 의학사상(醫學思想)에 대한 연구(硏究) [약리설(藥理設)을 중심(中心)으로])

  • Lim, Jin Seok;Park, Chan Kuk
    • Journal of Korean Medical classics
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    • v.9
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    • pp.381-429
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    • 1996
  • Choo-Joo(鄒澍;1790-1844) was the medicine scholar who lived in the late peroid of the Chung-Dynasty and wrote "Bon-Kyung-So-Jeung(本經疏證)", "Bon-kyung-Sok-So(本經續疏)", "Bon-Kyng-Seo-So-Yo(本經序疏要)". In the books mentioned above, He annotated the chief effectiveness of herbal medicine(本草) which had been presented on "Shin-Nong-Bon-Cho-Kyung(神農本草經)" and "Myoung-Eui-Byul-Lok(名醫別錄)". He defined medical action of 315 herb-items with the many theories of various scholars. Scholars whom Choo-Joo has qoutated belong to the school of study of Chinese classics, and they have regarded "Hwang-Je-Nae-Kyung(黃帝內經)", "Shin-Nong-Bon-Cho-Kyung(神農本草經)" and "Sang-Han-Lon(傷寒論)" as great important cannon and have lived during the Myoung Chung Dynasty. The distinctive character of Choo-Joo belongs to similar academic traditions. It seems that he was appected mainly by "Bon-Cho-Gang-Mok(本草綱目)" written by Lee-Si-Jin(李時珍), Mok-Jung-Soon(繆仲淳)'s "Sin-Nonng-Bon-Cho-Kyung-So(神農本草經疏)", You-Yak-Guem(劉若金)'s "Bon-Cho-Sul(本草述)" and Yang-Si-Tae(楊時泰)'s "Bon-Cho-Sul-Gu-Won(本草述鉤元)". He contributed in two big sides. First, Choo-Joo(鄒澍) have achieved much contribution in biliographical study of Chinese classics(考證學). He analyzed the medical theory of herb-medicine, combining with "Nae-Kyung(內經)", "Sang-Han-Lon(傷寒論)" and many theory of various scholars in order to make research on the chief effectiveness that had been presented in "Shin-Nong-Bon-Cho-Kyung(神農本草經)". Therefore the practical application of medical theory and term which had been represented on classics were offered. Secondary, Choo-joo did great accomplishment in pharmacology. The point of his theory was grasping the effect of a medicine through distinctive one beyond general feature. He set up standards that grasp distintive feature as form, color, energy and taste, place of production and temper. And on the basis of these standards he investigated distinctive feature on various fields, then he induced 'the Uem-Yang-0-Haeng Theory(陰陽五行說)' from distictions. According to the these method of classification, form(形) stand for the resultant shape of herbal function, color(色) represent the active direction of herb, energy and taste(氣味) imply the ultimate active function of herb, the place of production(産地) and the period of occurrence(發生時期) symbolize symptoms. When he applied these method to seek for effetiveness, he regarded the field which revealed most representative feature as of great importance, and Combining remained distinctions with one another, he determined more accurate medicinal value. These method of obsevation solved contradiction which occured by equaly appling all medical herbs for the regular standard. The most important theory that represented in Choo-Joo(鄒澍) is to induce and to certify the distintive feature of herb into the 'Uem-Yang-0-Haeng Theory'. That is, concluded as "spring(生), growing(長), change(化), collecting(收) and storing(藏)". As the results of these studies, he made clear the action of medicine more concretly and made 'the Uem-Yang-0-Haeng Theory(陰陽五行說)' more concret and actual for applying. And he contrbuted to establish the standard for grasping the effect of medicines.

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