• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2983-2988
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

• 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.

• Journal of the Korean Association of Oral and Maxillofacial Surgeons
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• v.41 no.3
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• pp.133-138
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• 2015

Objectives: To evaluate the influence of the type of osteotomy in the inferior aspect of the mandible on the mechanical performance. Materials and Methods: The study was performed on 20 polyurethane hemimandibles. A sagittal split ramus osteotomy (SSRO) was designed in 10 hemimandibles (group 1) with a vertical osteotomy in the buccal side (second molar level) and final osteotomy was performed horizontally on the lingual aspect, while the mandible body osteotomy was finalized as a straight osteotomy in the basilar area, perpendicular to the body. For group 2, the same osteotomy technique was used, but an oblique osteotomy was done in the basilar aspect of the mandibular body, forming continuity with the sagittal cut in the basilar area. Using a surgical guide, osteosynthesis was performed with bicortical screws using an inverted L scheme. In both groups vertical compression tests were performed with a linear load of 1 mm/min on the central fossa of the first molar and tests were done with models made from photoelastic resin. Data were analyzed using Student's t-test, establishing a statistical significance when P<0.05. Results: A statistical difference was not observed in the maximum displacements obtained in the two osteotomies (P<0.05). In the extensiometric analysis, statistically significant differences were identified only in the middle screw of the fixation. The photoelastic resin models showed force dissipation towards the inferior aspect of the mandible in both SSRO models. Conclusion: We found that osteotomy of the inferior aspect did not influence the mechanical performance for osteosynthesis with an inverted L system.

• Journal of the Korean Geotechnical Society
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• v.20 no.8
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• pp.135-145
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• 2004

In this study, the behavior of unpropped diaphragm walls on decomposed granite soil was investigated through centrifugal and numerical modelling. Centrifuge model tests were performed by changing the interval distance of surcharge. Excavation was simulated during the centrifuge tests by operating a solenoid valve that allowed the zinc chloride solution to drain from the excavation. In these tests, ground deformation, wall displacement and bending moment induced by excavation were measured. FLAC program which can be able to apply far most geotechnical problems was used in the numerical analysis. In numerical simulation, Mohr-Coulomb model fur the ground model, an elastic model for diaphragm wall were used for two dimensional plane strain condition. From the results of model tests, failure surface was straight line type, the ground of retained side inside failure line had downward displacement to the direction of the wall, and finally the failure was made by the rotation of the wall. The angle of failure line was about 67 ∼ 74$^{\circ}$, greater than calculated value. The locations of the maximum ground settlement obtained from model tests and analysis results are in good agreements. The displacement of wall and the change of the embedment depth is likely to have linear relationship.

• Bulletin of the Korean Chemical Society
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• v.34 no.10
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• pp.2877-2882
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• 2013

Second-order rate constants ($k_{Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ${\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with ${\beta}_{lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The ${\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the ${\alpha}$-effect (i.e., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the ${\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent ${\alpha}$-effect trend (i.e., TS effect).

• Economic and Environmental Geology
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• v.6 no.4
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• pp.201-216
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• 1973

Being believed thus far to be distributed in the wide areas in the vicinity of Seoul, the capital city of Korea, the Yonchon System in its type locality in Yonchon-gun from which the name derived was never previously traced down or correlated to the Precambrian metamorphic complex in Seoul area where the present study was carried out. Due to in accessibility to Yonchon area, the writer also could not trace the system down to the area studied so as to correlate them. The present study endeavored to differentiate general stratigraphy and interprete the structure of the metamorphic complex in the area. In spite of the complexity of structure and rapid changes in lithofacies of the complex, it was succeeded to find out the key bed by which the stratigraphy and structure of the area could be straightened out. The keybeds were the Buchon limestone bed in the western parts of the area; Daisongri quartzite bed cropped out in the southeastern area; Jangrak quartzite bed scattered in the several localities in the northwest, southwest, and eastern parts of the area; and Earn quartzite bed isolated in the eastern part of the area. These keybeds together with the broad regional structure made it possible to differentiated the Precambrian rocks in ascending order into the Kyonggi metamorphic complex, Jangrak group and Chunsung group which are in clinounconformable relation, and the first complex were again separated in ascending order into Buchon, Sihung, and Yangpyong metermorphic groups. Althcugh it has being vaguely called as the Yonchon system thus far, the Kyonggi metamorphic complex have never been studied before. The complex might, however, belong to early to early-middle Precambrian age. The Jangrak and Chunsung group were correlated to the Sangwon system in North Korea by the writer (1972), but it became apparent that the rocks of the groups have different lithology and highly metamorphosd than those of the Sangwon system which has thick sequence of limestone and slightly metamorphosed. Being deposited in the margin of the basin, it is natural that the groups poccess terrestrial sediments rather than limestone, yet no explanation is at hand as to what was the cause of bringing such difference in grade of metamorphism. Thus the writer attempted to correlate the both groups to those of pre-Sangwon and post-Yonchon which might be middle to early-late Precambrian time. Judging from difference in grade of deformation and unconformity between the Kyonggi metamorphic complex, Jangrak group, and Chunsung group, three stages of orogeny were established: the Kyonggi, Jangrak orogenies, and Chunsung disturbance toward younger age. It is rather astonishing to point out that the structure of these Precambrian formations. was not effected by Daebo orogeny of Jurassic age. The post-tectonic block faulting was accompanied by these orogenies, and in consequence NNE and N-S trending faults were originated. These faulting were intermittented and repeated until Daebo orogeny at which granites intruded along these faults. The manifestation of alignment of these faults is indicated by the parallel and straight linear development of valleys and streams in the Kyonggi Massifland.

• Analytical Science and Technology
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• v.11 no.3
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• pp.179-188
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• 1998

The capacity factor of fifteen phenol derivatives was determined with respect to the concentration of ${\alpha}$- or ${\beta}$-cyclodextrin [CD], the type as well as the content of organic solvent in the mobile phase, and the temperature. The effect of the inclusion complex formation between solutes and ${\alpha}$- or ${\beta}$-cyclodextrin on their retention and selectivity has been investigated. The inclusion effect of ${\beta}$-cyclodextrin was the most effective in aqueous methanol, whereas only a poor effect was observed in aqueous tetrahydrofuran and aqueous acetonitrile. A plot of the reciprocal of the capacity factor against $[CD]_T$ gives a straight line and the dissociation constant, $K_D$ of the inclusion complex can be calculated from the slope. It was possible to estimate the $k_D$ values in 100% water from a linear plot of $pK_D$ vs. water content in the solution by extrapolation. The separation factor, ${\alpha}$, of two compounds has been found to be affected not only by the $[CD]_T$ but also by their $K_D$ values. Under optimum conditions, some mixtures of phenol derivatives were able to separate successfully.

• Korean Journal of Plant Taxonomy
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• v.34 no.2
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• pp.97-118
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• 2004

A comparative anatomical and ultrastructural study was undertaken to investigare on the leaf epidermis by light microscopy (LM) and scanning electron microscopy (SEM). On the basis of results from this study, it was grasped major characters of taxa and variation range of each character on the level of species, section and subgenus respectively. The shape of leaf epidermal cell was oblong to linear, which was varied by each taxon. Epidermal cell of taxa in sects. Microscordum, Anguinum, and Rhizirideum, which had wide leaf blade, oblong instead of linear shape in others examined taxa in this study. The leaf of taxa in sect. Anguinum was hypostomatic, while the rest of taxa had amphistomatic leaf. This was also one of characters which could discriminate taxa of sect. Anguinum from others. The guard cell in investigated taxa had not so much variation in the respect of its size. The number of stomata per unit area reduced by increasing size of epidermal cell, the fewest number of stomata per unit area was found in the taxa of sect. Anguinum. The type of stomatal apparatus of observed all taxa was anomocytic. It was found to know ultrastructural variation in the epidermal cell, like as patterns of sculpture on the cell wall, and features of deposition of wax by SEM. There were no depositions of wax in the taxa of sect. Microscordum and Anguinum, but fine thread-like structures which were parallel or cross to axis was found on the surface of epidermal cell respectively. The patterns of sculpture on the cell were prominent straight in sects. Recticulato-bulbosa and Rhizirideum, discontinuous line in the sect. Oreiprason. The epicuticular wax had been deposited on the surface of its epidermal cell in all taxa except sects. Microscordum and Anguinum.

• Economic and Environmental Geology
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• v.47 no.6
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• pp.571-588
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• 2014

It consists of the Precambrian Jirisan metamorphic complex and Sancheong anorthosite complex and the Mesozoic granitoids which intrude them in the Sancheong area, the Jirisan province of Yeongnam massif, Korea. The study area is located in the western part of the stock-type Sancheong anorthosite complex. We performed a detailed fieldwork on the Sancheong anorthosite (SA) and Fe-Ti ore body (FTO) which constitute the Sancheong anorthosite complex, and reinterpreted the origin of FTO foliation and the genetic relationship between them from the foliations, shear zones, occurrences of the SA and FTO. The new structural characteristics between them are as follows: the multilayer structures of FTO, the derived veins of straight, anastomosing uneven types and block structures related to the size reduction of SA, the gradual or irregular boundaries of SA blocks and FTO showing bulbous lobate margins and comb structures, the FTO foliation and linear arrangements of flow occurrence which is not ductile shear deformation, the discontinuous shear zone of SA, the orientation of FTO foliations parallel to the boundaries of SA blocks, the predominance of FTO foliations toward the boundaries of SA blocks and being proportional to the aspect ratio of plagioclase xenocrysts and SA xenoblocks, and the flow folding structures of FTO foliation. Such field evidences indicate that the SA is not fully congealed when the FTO is melt and the fracturing of partly congealed SA causes the derived veins of FTO and the size reduction of SA. Also the gradual or irregular boundaries of SA blocks and FTO result from the mutual reaction between the not fully congealed SA blocks and the FTO melt, and the FTO foliation is a magmatic foliation which was formed by the interaction between the FTO melt and the partly congealed SA blocks. Therefore, these suggest that the SA and FTO are not formed from the intrusion of different magmas in genesis and age but from a coeval and cogenetic magma through multiple fractionation. We predict that the FTO will show an very irregular occurrence injected along irregular fractures, not the regular occurrence like as the intrusive vein and dike. It can be applied to the designing of Fe-Ti mineral resource exploration in this area.