• Bulletin of the Korean Chemical Society
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• 제6권6호
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• pp.362-366
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• 1985

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

• Bulletin of the Korean Chemical Society
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• 제17권4호
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• pp.353-357
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with Z-substituted phenoxides in absolute ethanol at 25.0±0.1 ℃. The nucleophilic substitution reaction gives both S-O bond and C-O bond cleavage products. The extent of S-O bond cleavage increases significantly with increasing electron withdrawing ability of the sulfonyl substitutent X, while that of the C-O bond cleavage is independent on the electronic effect of the substituent. On the contratry, the effect of the substituent Z in the nucleophilic phenoxide is more significant for the C-O bond cleavage than for the S-O bond cleavage. Aminolyses of 2,4-dinitrophenyl benzenesulfonate (1) with various 1°, 2° and 3°amines have revealed that steric effect is little important. The extent of S-O bond cleavage increases with increasing the basicity of the amines, but decreases with increasing the basicity of the nucleophilic aryloxides, indicating that the HSAB principle is not always operative. Besides, reactant and solvent polarizability effect has also been found to be an important factor in some cases but not always to influence the reaction site.

• 한국진공학회지
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• 제6권S1호
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• pp.16-22
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• 1997

ion beam processing of materials for medical application has gained increasing interest in the last decade and the implantation of nitrogen into TI-6AI-4V to improve corrosive-wear performance is currently used for processing of total hip and knee joints. Oxides and nitrides of Ti, Zr, Al, Cr were deposited on TI-6AI-4V substrates by DC magnetron sputtering dual ion beam sputtering and ion beam assisted deposition. The cytotoxicity of these films were investigated by MTT method and showed comparable to untreated TI-6AI-4V Plasm-sprayed hydroxyapatite(HAp) coatings showed excellent cytotoxicity regardless of heat treatment. intermediate layer coatings of nitrides and oxides increased the bond strength of HAp to substrate by intrdducing chemical bond at interface. Heat treatment of HAp coatings also improved the chemical bond at interfaces and increased the bond strength of untreated TI-6AI-4V to 16.4 kg/$\textrm{cm}^2$ but still lower than 33.1 kg./$\textrm{cm}^2$ of ir oxide as a imtermediate layer caoting.

• 대한치과기공학회지
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• 제37권4호
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• pp.219-227
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• 2015

Purpose: The purpose of this study was to evaluate the effect of the chemical surface treatment on the flexural bond strength of heat curing denture base resin and reliners. Methods: Denture base resin surface was treated with MMA 95% and TEGDMA 5%, MMA 95% and silane coupling agent 5%, heat curing resin monomer. After denture reliners were injected, flexural bond strength was measured. Results: The repair resin of Vertex SC was higher than Lang, hard reliner of Kooliner was higher than Rebase. Soft reliner of Dura base and Coe-soft showed differently according to the surface treatment. The all chemical treatment groups on Vertex SC were significantly higher than control(p<0.05). In Lang group, 5% MPS treated group showed significantly higher flexural bond strength than others(p<0.05). In Kooliner group, all chemical treatment groups showed significantly higher than control(p<0.05). In Rebase group, the 5% MPS and the monomer denture base resin treated groups showed significantly higher than others(p<0.05). In Dura base group, 5% MPS treated group showed significantly higher flexural bond strength than others(p<0.05). In Coe-soft group, all treated groups were significantly higher than control group(p<0.05). Conclusion: TEGDMA, MPS, and the monomer of heat-cured denture base resin were effective to improve the bond strengths between denture base and denture relining materials. Especially, 5% MPS expected to strengthen effectively the bonding property of denture base and denture reliners within the results of this study.

• Bulletin of the Korean Chemical Society
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• 제27권4호
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• pp.495-502
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• 2006

Intramolecular energy flow and C-$H_{methyl}$ and C-$H_{ring}$ bond dissociations in vibrationally excited toluene in the collision with HF have been studied by use of classical trajectory procedures. The energy lost by the vibrationally excited toluene upon collision is not large and it increases slowly with increasing total vibrational energy content between 20,000 and 45,000 $cm ^{-1}$. Above the energy content of 45,000 $cm ^{-1}$, however, energy loss decreases. Furthermore, in the highly excited toluene, toluene gains energy from incident HF. The temperature dependence of energy loss is negligible between 200 and 400 K. Energy transfer to or from the excited methyl C-H bond occurs in strong collisions with HF transferring relatively large amount of its translational energy (>> $k_BT$) in a single step, whereas energy transfer to the ring C-H bond occurs in a series of small steps. When the total energy content $E_T$ of toluene is sufficiently high, either C-H bond can dissociate. The C-$H_{methyl}$ dissociation probability is higher than the C-$H_{ring}$ dissociation probability. The dissociation of the ring C-H bond is not the result of the intermolecular energy flow from the direct collision between the ring C-H and HF but the intramolecular flow of energy from the methyl group to the ring C-H stretch. The C-$H_{ring}$${\cdot}{\cdot}{\cdot}$HF interaction is not important in transferring energy and in turn bond dissociation.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1481-1490
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• 2005

Carbon-carbon single bond-forming reaction is the most useful and fundamental reaction in organic synthesis. Most of the basic carbon-carbon single bond-forming reactions, thus, developed in the past. In these respects, conceptually new C-C bond formation reaction can be highlighted. The Baylis-Hillman reaction was found at the early 1970’s. However, extensive studies on this highly potential reaction were started only before 15 years. This review has been written to shed more lights to the importance of Baylis-Hillman reaction. We have focused mainly on the reaction mechanism, conceptually related reactions, and chemical transformations of the Baylis-Hillman adducts.

• 대한화학회지
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• 제20권2호
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• pp.111-117
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• 1976

Methyl benzamidoxime의 C=N 결합에 의한 configuration 과 N-O 및 C-N 결합에 대한 conformation 에 관하여 확장 Huckel 분자궤도법 계산을 실시하였다. 계산 결과는 C-N 결합의 conformation이 sp-형이면 E-configuration이 Z-configuration보다 더 안정하다. ap-형이면 Z-configuration이 더 안정하다. C=N 결합의 configuration과 C-N 의 conformation이 같으면 N-O의 conformation이 ap-형인 것이 더 안정하다. 이 안정화 에너지의 대부분은 정전기적인 원자간에 힘에 기인하는 것임을 밝혔다.

• Bulletin of the Korean Chemical Society
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• 제4권1호
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• pp.41-44
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• 1983

The chlorine addition and Diels-Alder cycloaddition of cyclopentadiene to 1, 4-benzoquinone-4-(O-methyloxime) have been studied MO theoretically. It has been shown that the reactions occur predominantly to the quinone ring double bond which is oriented anti to the nitrogen lone pair due to an n-${\sigma}^*$ interaction between the nitrogen lone pair, n, and the app. vicinal bond, causing the ${\pi}$ bond to be weakened and destabilized due to the less conjugation from reduced delocalization.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.211-213
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• 1991

The ground state of the oxygen molecule is calculated by various methods of coupled cluster approaches and many body perturbation theory using a double zeta plus polarization basis set and the UHF reference state. All the methods employed are capable of describing the oxygen molecule near the equilibrium bond length and the separated atom, but do not correctly depict the breaking of the multiple bond. For this basis set, including more correlations does not necessarily improve the agreement with experiment for molecular properties such as bond lengths and dissociation energies.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 2006년도 춘계 학술발표회 논문집(II)
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• pp.225-228
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• 2006

To clarify the one body behavior of reinforcing bar and concrete, it is important to investigate bond characteristics between two materials. Bond strength is decided by applied force and interface area between reinforcing bar and concrete. And, the resultant force of chemical adhesive force, frictional force, and mechanical interaction are to be main factors. Property of concrete influences on chemical adhesive force and frictional force; bond strength is decreased by corrosion of reinforcing bar, as the result, durability is also decreased. In this study, to confirm bond characteristics with property of concrete, w/c ratio and blending of mineral admixture were selected as the main test parameters. The results obtained from this study will be used as the basic data for bond characteristics with corrosion.