• Title/Summary/Keyword: Bond mechanism

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Adsorption and Removal Mechanism of Dissolved Inorganic Nutrients in Seawater by Yellow Loess (황토살포에 의한 해수중 영양염류의 흡착제거기구)

  • Kim Pyoung Joong;Heo Seung;Yun Seong Jong
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.35 no.2
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    • pp.146-154
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    • 2002
  • To assess the adsorption and removal mechanism of dissolved inorganic nutrients in seawater by scattering yellow loess, a laboratory experiment was conducted for the change of nutrient concentration in seawater during the course of time depending on particle size and scattered concentration of the yellow loess. Twenty four hours after the addition of yellow loess in the size range of 0 $\mu$m to 500 $\mu$m in seawater, the removal rate of dissolved inorganic phosphorus (DIP) was increased with increasing amount of yellow loess. There was little difference among the removal rates depending on the size of yellow loess. On average, $26\%$ of dissolved inorganic silicate was reduced for the same period. No greate difference among the removal rate depending on both size and amount of yellow loess was found. Our results suggested that the removal mechanism of DU seemed to be associated with mostly the chemical bond with iron. More than $99\%$ of initial DU concentration was likely to be removed by this mechanism. In the case of inorganic dissolved silicate, the removal mechanism was likely to be attributed to a cation exchange between the yellow loess and seawater.

Solvation in Mixed Solvent (III). Solvatochromic Analysis for the Solvent Effect of Binary Mixed Solvent (혼합용매에서의 용매화 (제3보). 이성분 혼합용매 중에서 용매효과에 대한 분광용매화 분석)

  • Lee, Ik-Choon;La, Sang-Mu;Lee, Bon-Su;Sohn, Se-Chul
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.210-216
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    • 1984
  • Solvatochromic comparison methods were applied to determine Taft's solvent parameters, ${\pi}^{\ast}$(solvent polarity-polarizability), ${\alpha}$(solvent hydrogen bond donor acidity) and ${\beta}$ (solvent hydrogen bond acceptor basicity) for MeOH-MeCN solvent mixtures. Swain's solvent parameters A(anion solvation scale) and B(cation solvation scale) were also determined by least square fitting of kinetic data in the same binary solvent mixtures. It was found that: (i)${\beta}$ depends on the basicity of the solvent and increases with the MeOH content owing to the increase in polymeric structure of methanol; (ii) ${\pi}^{\ast}$depends on the dipole moment of the solvent and increases with the MeCN content of the solvent; (iii) ${\alpha}$ increases rapidly with the MeOH content as the hydrogen bond donor acidity of the solvent mixtures increases. Taft's reaction constants a and s and Swain's reaction constants a and b were determined for the reactions reported from our laboratory previously using solvent parameters determined in this work. No meaningful inter-relationship was found between the two set of reaction parameters, but a good linear correlation was found between the ratios a/s and a/b. Solvent effect on the reaction mechanism, substituent effect and leaving group ability were examined in the light of these reaction constants ratios.

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A Fundamental Study on Shearing/Bonding Characteristics of Interface Between Rock Mass and Backfills in Mine Openings (폐광산 채움재와 암반 경계부의 전단 및 접합특성에 관한 기초 연구)

  • Kim, Byung-Ryeol;Lee, Hyeon-woo;Kim, Young-Jin;Cho, Kye-Hong;Choi, Sung-Oong
    • Tunnel and Underground Space
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    • v.31 no.6
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    • pp.623-646
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    • 2021
  • As the demand for electric power increases with acceleration of electrification at home and abroad, the needs for coal-fired electrical power plant are accordingly increased. However, these coal-fired electrical power plants induce also many environmental problems such as increase of air pollutants, increase of possibility of land contamination by reclamation of coal ash, even though these power plants have a good economical efficiency. In case of a by-product of coal-fired electrical power plants, only 70% of them are recycled and the remaining 30% of by-product are fully buried in surrounding ground. Consequently, this study deals with coal ash backfilling mechanism in abandoned mine openings for the purposes of increasing the coal ash recycling rate as well as securing the mine area stability. In order to analyze the backfill and ground reinforcement by interaction between rock mass and backfills, the copying samples of discontinuous surface with different roughnesses were produced for bond strength tests and direct shear tests. And statistical analysis was also conducted to decide the characteristics of bond and shear behavior with joint roughness and their curing day. Numerical simulations were also analyzed for examining the effect of interface behavior on ground stability.

Repair of UV-induced Cyclobutane Pyrimidine Dimers in Human Mitochonrial DNA-less Cells

  • Ikushima, Takaji;Gu, Ning;Tanizaki, Yuichi
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.479-481
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    • 2002
  • UV-induced DNA damage causes cell killing and mutations leading to carcinogenesis. In normal human cells, UV damage such as cyclobutane pyrimidine dimers (CPDs) and primidine-prymidone (6-4) photoproducts are mainly repaired by nucleotide excision repair mechanism. The molecular processes have been well characterized recently. To know the influence of mitochondrial genome on the nucleotide excision repair mechanism against CPDs, we comparatively examined the production of CPDs by UVC irradiation and their repair kinetics in human cells completely lacking mitochondrial DNA (mtDNA) and the parental HeLa S cells. Whole DNA extracted from the cells exposed to UVC was treated with T4-endonuclease V to break the phosphodiester bond adjacent to CPDs. The DNA was electrophoresed in a denaturing agarose gel, which was visualized by ethidium bromide staining. The relative amount of CPDs was determined by image analysis using NIH Image software. MtDNA- less (rho-O) cells were apparently more sensitive to UVC than HeLa S cells, while the level of induction of CPDs in rho-O and HeLa cells was comparable. The repair of CPDs was less efficient in rho-O cells compared with HeLa cells. The residual amount of CPDs after 24-h repair was larger in rho-O cells than in HeLa cells where more than 90 % of CPDs were repaired by then. The non-repaired CPDs would lead to apoptosis in rho-O cells. These results suggest that mitochondrial genome may contribute to some ATP-dependent steps in nucletide excision repair by supplying sufficient ATP which is generated through a respiratory chain in mitochondria.

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Adsorbed Carbon Formation and Carbon Hydrogenation for CO2 Methanation on the Ni(111) Surface: ASED-MO Study

  • Choe, Sang-Joon;Kang, Hae-Jin;Kim, Su-Jin;Park, Sung-Bae;Park, Dong-Ho;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1682-1688
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    • 2005
  • Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.

Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.3947-3951
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    • 2011
  • The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

Kinetic Study on Aminolysis of 4-Pyridyl X-Substituted Benzoates: Effect of Substituent X on Reactivity and Reaction Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1907-1911
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    • 2011
  • A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

THE EFFECTS OF SEALING ON THE PLASMA-SPRAYED OXIDE-BASED COATINGS

  • Kim, Hyung-Jun;Sidoine Odoul;Kweon, Young-Gak
    • Proceedings of the KWS Conference
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    • 2002.10a
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    • pp.53-58
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    • 2002
  • Electrical insulation and mechanical properties of the plasma sprayed oxide ceramic coatings were studied before and after the sealing treatment of the ceramic coatings. Plasma sprayed A1$_2$O$_3$-TiO$_2$ coating as the reference coating was sealed using three commercial sealants based on polymer. Penetration depth of the sealants to the ceramic coating was evaluated directly from the optical microscope using a fluorescent dye. It is estimated that the penetration depth of the sealants to the ceramic coating is from 0.2 to 0.5 mm depending on the sealants used. The preliminary test results with a DC puncture tester imply that the dielectric breakdown voltage mechanism of plasma sprayed ceramic coatings has been determined to be a corona mechanism. Dielectric breakdown voltage of the as-sprayed and as-ground samples have shown a linear trend with regard to the thickness showing an average dielectric strength of 20 kV/mm for the thickness scale studied. It is also shown that grinding the coating before sealing and adding fluorescent dye do not agent the penetration depth of sealants. All of the microhardness, two-body abrasive wear resistance, bond strength, and surface roughness of the ceramic coating after the sealing treatment are improved. The extent of improvement is different from the sealants used. However, three-point bending stress of the ceramic coating after the sealing treatment is decreased. This is attributed to the reduced micro-crack toughening effect since the cracks propagate easily through the lamellar of the coating without crack deflection and/or branching after the sealing treatment.

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Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde

  • Lu, Xiuhui;Li, Yongqing;Ming, Jingjing
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3690-3694
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    • 2013
  • The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

Semi-Empirical Prediction of Crack Width of the Strengthened Bridge Deck with External Bonding Plastic (외부부착 보강된 교량 바닥판 균열폭의 반경험적인 예측)

  • 심종성;오홍섭
    • Journal of the Korea Concrete Institute
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    • v.14 no.2
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    • pp.231-238
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    • 2002
  • Dry shrinkage md temperature change cause to develope concrete bridge decks on main girders have initial unidirectional cracks in longitudinal or transverse direction. As they receive traffic loads, the crack gradually propagate in different directions depending on the concrete dimension and reinforcement ratio. Since existing equations that predict crack width are mostly based on the one directional bond-slip theory, it is difficult to determine the actual crack width of a bridge deck with varying the spacing of rebar or strengthening material and to estimate the improvement rate in serviceability of the strengthened bridge deck. In this study, crack propagation mechanism is identified based on the test results and a new crack prediction equation is proposed for evaluation of serviceability. Although more accurate results are derived using the proposed equation, the extent of error is increased as the strain of the rebar or the strengthening material increases after the yielding of rebar Therefore, further research is required to better predict the crack width after the rebar yields under fatigue loading condition.