• Title/Summary/Keyword: Addition-Elimination

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Hydrolysis Mechanism of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl Chloride Derivatives (N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl Chloride 유도체의 가수분해 반응 메카니즘)

  • Kwon, Ki-Sung;Song, Yun-Yi
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.650-656
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    • 1995
  • Rate Constants of hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides were determined by UV spectrophotometry in 50% (v/v) aqueous methanol at 25$^{\circ}C.$ On the basis of rate equation, substituent effect, solvent effect, salt effect, thermodynamic parameters and hydrolysis product analysis, it may be concluded that the hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides proceed through $S_N1$ mechanism via azocarbonium ion intermediate below pH 9.0, while aebove pH 10.0 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism.

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Correlation of the Rates of Solvolysis of 4-Morpholinecarbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Kim, Ran;Ali, Dildar;Lee, Jong-Pal;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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    • pp.1963-1967
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    • 2010
  • The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

Reactions of 4-Nitrophenyl 2-Thiophenecarboxylates with R2NH/R2NH2+ in 20 mol % DMSO (aq). Effects of 5-Thienyl Substituent and Base Strength

  • Pyun, Sang Yong;Cho, Bong Rae
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2036-2040
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    • 2013
  • Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.

Clean Technology in Chemical Industries (화학산업의 청정기술 개발)

  • Kim, Younghun;Yi, Jongheop;Kim, Hwayong;Rhee, Hyun-Ku
    • Clean Technology
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    • v.7 no.1
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    • pp.1-12
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    • 2001
  • A variety of international treaties have been developed for the world-wide control of hazardous chemicals, including production, transportation, use and disposal. Those conventions would be appeared as a barrier for the international trade. In particular, chemical industries in korea would face a serious problem unless a proper measure should be provided. One of the solutions is to develop a clean technology including elimination and/or source reduction of hazardous chemicals. In this study, international environmental treaties and management status of hazardous chemicals in korea are reviewed. In addition, strategies for the development of clean technologies are suggested.

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MLPPI Wizard: An Automated Multi-level Partitioning Tool on Analytical Workloads

  • Suh, Young-Kyoon;Crolotte, Alain;Kostamaa, Pekka
    • KSII Transactions on Internet and Information Systems (TIIS)
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    • v.12 no.4
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    • pp.1693-1713
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    • 2018
  • An important technique used by database administrators (DBAs) is to improve performance in decision-support workloads associated with a Star schema is multi-level partitioning. Queries will then benefit from performance improvements via partition elimination, due to constraints on queries expressed on the dimension tables. As the task of multi-level partitioning can be overwhelming for a DBA we are proposing a wizard that facilitates the task by calculating a partitioning scheme for a particular workload. The system resides completely on a client and interacts with the costing estimation subsystem of the query optimizer via an API over the network, thereby eliminating any need to make changes to the optimizer. In addition, since only cost estimates are needed the wizard overhead is very low. By using a greedy algorithm for search space enumeration over the query predicates in the workload the wizard is efficient with worst-case polynomial complexity. The technology proposed can be applied to any clustering or partitioning scheme in any database management system that provides an interface to the query optimizer. Applied to the Teradata database the technology provides recommendations that outperform a human expert's solution as measured by the total execution time of the workload. We also demonstrate the scalability of our approach when the fact table (and workload) size increases.

Improvement of Image Processing Technique for Drop Size Measurement (입경 측정을 위한 영상 처리 기법의 개선)

  • Kim, Joo Youn;Chu, Jeong Ho;Lee, Sang Yong
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.22 no.8
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    • pp.1152-1163
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    • 1998
  • In the present work, the image processing technique for measurement of drop sizes has been improved. Firstly, the local processing concept was adopted in addition to the global processing technique to take account of non-uniformity of the illumination intensity ; thereby, basically, the measurement error can be reduced. Also, the unfocussed image of drops can be eliminated more precisely since the elimination process is based on the local normalized contrast. Secondly the algorithms to process the partially detected or overlapped drop images and the non-spherical drop images were developed. Finally, the improved algorithm was tested by using an artificially prepared image-frame, where the partial or overlapped particles and the non-spherical particles are mixed with the normal spherical ones (with their true size-distributions known a priori). The results showed that both the recognition rate of the number of particles and the measurement accuracy were improved prominently.

Postnatal Development of Subcallosal Zone Following Suppression of Programmed Cell Death in Bax-deficient Mice

  • Kim, Woon Ryoung;Sun, Woong
    • Development and Reproduction
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    • v.17 no.3
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    • pp.179-186
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    • 2013
  • Neural stem cells are found in adult mammalian brain regions including the subgranular zone (SGZ) of the dentate gyrus (DG) and the subventricular zone (SVZ). In addition to these two regions, other neurogenic regions are often reported in many species. Recently, the subcallosal zone (SCZ) has been identified as a novel neurogenic region where new neuroblasts are spontaneously generated and then, by Bax-dependent apoptosis, eliminated. However, the development of SCZ in the postnatal brain is not yet fully explored. The present study investigated the precise location and amount of neuroblasts in the developing brain. To estimate the importance of programmed cell death (PCD) for SCZ histogenesis, SCZ development in the Bax-knockout (KO) mouse was examined. Interestingly, an accumulation of extra neurons with synaptic fibers in the SCZ of Bax-KO mice was observed. Indeed, Bax-KO mice exhibited enhanced startle response to loud acoustic stimuli and reduced anxiety level. Considering the prevention of PCD in the SCZ leads to sensory-motor gating dysfunction in the Bax-KO mice, active elimination of SCZ neuroblasts may promote optimal brain function.

Fabrication of Nanoporous Carbon Fibers by Electrospinning (상 분리 폴리머 혼합액의 전기 방사에 의한 나노 포러스 탄소 파이버 제작)

  • Kim, Hong-Yeun;Lee, Dae-Hee;Moon, Joo-Ho
    • Korean Journal of Materials Research
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    • v.19 no.10
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    • pp.562-568
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    • 2009
  • Electrospinning is a technique that produces sub-micron sized continuous fibers by electric force from polymer solutions or melts. Due to its versatile manufacturability and the cost effectiveness, this method has been recently adopted for the fabrication of one-dimensional materials. Here, we fabricated polyacrylonitrile (PAN) polymer fibers, from which uniform carbon fibers with diameters of 100-200 nm were obtained after carbonization at 800 $^{\circ}C$ in N$_2$. Special emphasis was directed to the influence of the phase separated polymer solution on the morphology and the microstructure of the resulting carbon fiber. The addition of poly(stylene-co-acrylonitile) (SAN) makes the polymer solution phase separated, which allows for the formation of internal pores by its selective elimination after electrospinning. XPS and Raman Spectroscopy were used to confirm the surface composition and the degree of carbonization. At the PAN:SAN = 50:50 in vol%, the uniform carbon fibers with diameters of 300$\sim$500 nm and surface area of 131.6 m$^2$g$^{-1}$ were obtained.

Transparent Ceramics for Visible/IR Windows: Processing, Materials and Characterization

  • Jung, Wook Ki;Ma, Ho Jin;Kim, Ha-Neul;Kim, Do Kyung
    • Korean Journal of Materials Research
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    • v.28 no.10
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    • pp.551-563
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    • 2018
  • Visible and IR windows require a combination of high optical transparency and superior thermal and mechanical properties. Materials, fabrication and characterization of transparent ceramics for visible/IR windows are discussed in this review. The transparent polycrystalline $Y_2O_3$, $Y_2O_3-MgO$ nanocomposites and $MgAl_2O_4$ spinel ceramics are fabricated by advanced ceramic processing and the use of special sintering technologies. Ceramic processing conditions for achieveing fully densified transparent ceramics are strongly dependent on the initial powder characteristics. In addition, appropriate use of sintering technologies, including vacuum sintering, hot-pressing and spark plasama sintering methods, results in outstanding thermal and mechanical properties as well as high optical transparency of the final products. Specifically, the elimination of light scattering factors, including residual pores, second phases and grain boundaries, is a key technique for improving the characteristics of the transparent ceramics. This paper discusses the current research issues related to synthesis methods and sintering processes for yttria-based transparent ceramics and $MgAl_2O_4$ spinel.

Cancer stem cell metabolism: target for cancer therapy

  • Chae, Young Chan;Kim, Jae Ho
    • BMB Reports
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    • v.51 no.7
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    • pp.319-326
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    • 2018
  • Increasing evidence suggests that cancer stem cell (CSC) theory represents an important mechanism underlying the observed failure of existing therapeutic modalities to fully eradicate cancers. In addition to their more established role in maintaining minimal residual disease after treatment and forming the new bulk of the tumor, CSCs might also critically contribute to tumor recurrence and metastasis. For this reason, specific elimination of CSCs may thus represent one of the most important treatment strategies. Emerging evidence has shown that CSCs have a different metabolic phenotype to that of differentiated bulk tumor cells, and these specific metabolic activities directly participate in the process of CSC transformation or support the biological processes that enable tumor progression. Exploring the role of CSC metabolism and the mechanism of the metabolic plasticity of CSCs has become a major focus in current cancer research. The targeting of CSC metabolism may provide new effective therapies to reduce the risk of recurrence and metastasis. In this review, we summarize the most significant discoveries regarding the metabolism of CSCs and highlight recent approaches in targeting CSC metabolism.