• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2219-2225
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• 2007

The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

• 한국정보디스플레이학회:학술대회논문집
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• 2006.08a
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• pp.772-775
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• 2006

Cinnamate polymers are well known photoreactive polymers due to [2+2] cycloaddition reaction of cinnamate side group. In this work, we have found that the cinnamate side groups could be also reacted by thermal energy, and this reaction is presumed to attribute to the radical reaction of carbon double bond in the cinnamate groups. Contrary to the photocycloaddition reaction of the cinnamate side groups, the thermal reaction of cinnamate side group was closely related to the flexibility of polymer backbone. The difference of the mechanism between the photocycloaddition reaction and thermal crosslinking reaction was confirmed by $^1H-NMR$$ and $^{13}C-NMR$ analysis of the model compound.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.63.2-63.2
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• 2015

Controlling and sensing spin states of magnetic molecules such as metallo-porphyrins at the single molecule level is essential for spintronic molecular device applications. Axial coordinations of diatomic molecules to metallo-porphyrins also play key roles in dynamic processes of biological functions such as blood pressure control and immune response. However, probing such reactions at the single molecule level to understand their physical mechanisms has been rarely performed. Here we present on our single molecule association and dissociation experiments between diatomic and metallo-porphyrin molecules on Au(111) describing its adsorption structures, spin states, and dissociation mechanisms. We observed bright ring shapes in NO adsorbed metallo-porphyrin compelxes and explained them by considering tilted binding and precession motion of NO. Before NO exposure, Co-porphryin showed a clear zero-bias peak in scanning tunneling spectroscopy, a signature of Kondo effect in STS, whereas after NO exposures it formed a molecular complex, NO-Co-porphyrin, that did not show any zero-bias feature implying that the Kondo effect was switched off by binding of NO. Under tunneling junctions of scanning tunneling microscope, both positive and negative energy pulses. From the observed power law relations between dissociation rate and tunneling current, we argue that the dissociations were inelastically induced with molecular orbital resonances. Our study shows that single molecule association and dissociation can be used to probe spin states and reaction mechanisms in a variety of axial coordination between small molecules and metallo-porphyrins.

• Computers and Concrete
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• v.2 no.6
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• pp.439-454
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• 2005

When deterioration of concrete is observed in a structure, it is highly desirable to determine the cause of such deterioration. Only by understanding the cause can an appropriate repair strategy be implemented to address both the cause and the symptom. In colder climates, bridge deck deterioration is often caused by chlorides from de-icing salts, which penetrate the concrete and depassivate the embedded reinforcement, causing corrosion. Bridge decks can also suffer from other deterioration mechanisms, such as alkali-silica reaction, freeze-thaw, and shrinkage. There is a need for a comprehensive and integrative system to help with the inspection and evaluation of concrete bridge deck deterioration before decisions are made on the best way to repair it. The purpose of this research was to develop a model to help with the diagnosis of concrete bridge deck deterioration that integrates the symptoms observed during an inspection, various deterioration mechanisms, and the probability of their occurrence given the available data. The model displays the diagnosis result as the probability that one of four deterioration mechanisms, namely shrinkage, corrosion of reinforcement, freeze-thaw and alkali-silica reaction, is at fault. Sensitivity analysis was performed to determine which probabilities in the model require refinement. Two case studies are included in this investigation.

• Korean Journal of Environmental Agriculture
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• v.12 no.3
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• pp.264-280
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• 1993

The environmental pollutions were a serious problem in Korea recently. So many researcher have studied the effect of environmental pollution on plants and agro-ecosystem, but the basic mechanisms of environmental stresses were various. One of the important mechanisms was oxidative stress caused by active toxic oxygen. The toxic oxygen was generated by several stresses, abnormal temperature, many xenobiotics, air pollutants, water stress, fugal toxin, etc. In the species of toxic oxygen which is primary inducer of oxidative stresses, superoxide, hydrogen peroxide, hydroxyl radical and singlet oxygen were representative species. The scavenging systems were divided into two groups. One was nonenzymatic system and the other enzymatic system. Antioxidants such as glutathione, ascorbic acid, and carotenoid, have the primary function in defense mechanisms. Enzymatic system divided into two groups; First, direct interaction with toxic oxygen(eg. superoxide dismutase). Second, participation in redox reaction to maintain the active antioxidant levels(eg. glutathione reductase, ascorbate peroxidase, etc.).

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2673-2678
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• 2014

The detailed mechanisms of the efficient $\small{L}$-proline and pyrrolidine catalyzed transamidation of acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) the mechanisms of two catalytic cycle reactions are similar. However, the rate-determining steps of their reactions are different for the whole catalytic process. One is the intramolecular nucleophilic addition reaction of 1-COM, the other is hydrolysis reaction of 2-C. (2) COOH group of $\small{L}$-proline is essential for efficient transamidation. The computational results are in good agreement with the experiment finding and mechanism resported by Rao et al. for $\small{L}$-proline-catalyzed synthesis of amidesin good to excellent yields.

• Journal of Photoscience
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• v.12 no.2
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• pp.101-107
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• 2005

Infrared multiphoton dissociation of $CHCl_2F$ was studied using $CO_2$ laser excitation. Three products, $C_2Cl_2F_2$, $C_2ClF_3$, and $C_2HClF_2$, were identified by the analysis of the gas mixture from the photoreaction of $CHCl_2F$. The dependence of the reaction probability on added Ar gas pressure and excitation laser pulse energy was investigated. At low pressure (< 10 torr), the reaction probability increased as Ar pressure increased due to the rotational hole-filling effect, while it diminished with the increase of Ar pressure at high pressure (> > 20 torr) due to the collisional deactivation. The ratio of two products $(C_2ClF_3/C_2Cl_2F_2)$ decreased at low pressure (< 10 torr) and increased at high pressure (> 20 torr) with the increase of Ar pressure. The log-log plot of the reaction probability vs. laser pulse energy (${\\phi}$) was found to have a linear relationship, and its slope decreased as the added Ar pressure was increased. The reaction mechanisms for product formation have been suggested and validated by experimental evidences and considering the energetics. Fluorine-chlorine exchange reaction in the intermediate complex has been suggested to explain the formation of $C_2ClF_3$.

• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.499-504
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• 2009

Metals have often played important roles to some enzymatic reactions that are essential to biological processes. Therefore many scientists have studied the reaction mechanisms of catalytic reactions in metaloenzymes for many years. Methane MonoOxygenase (MMO) is an enzyme that oxidize methane to methyl alcohol. Recently Tolman et al. studied a model reaction for MMO, which is a hydroxide transfer reaction in Bis-($\mu$-oxo)-dicopper complex, and suggested several possible mechanisms. Later a two-step mechanism, which is hydrogen transfer followed by hydroxide rebound, was proposed from theoretical studies. In this study we calculated the reactant, product, and the transition state structures, and energetics of the first hydrogen transfer reaction using various DFT methods including recently developed the MO6 family of DFT, namely, MO6, MO6L, and MO6-2X. We found that the M06/6-31G(d,p)/LANL2DZ method reproduce the experimental XRD structure of reactants very well. The TS structures, barrier heights, and reaction energies depend very much on the size of the basis sets.

• Journal of the Korean Academy of Child and Adolescent Psychiatry
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• v.20 no.3
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• pp.140-145
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• 2009

Objectives : This study explored the differences in their ego defense mechanisms between adolescents with conduct disorder and normal adolescents. Methods : Subjects were 35 adolescents with conduct disorder and 44 normal adolescents. The Ewha Defense Mechanism Test (EDMT), consisting of 200 items and 20 scales, was administered, to examine the defense mechanisms of both groups of adolescents. Results : Normal adolescents presented statistically significantly higher scores on the reaction formation, controlling, suppression, anticipation, dissociation, and distortion scales than did adolescents with conduct disorder. Zn addition, adolescents with conduct disorder used neurotic defense mechanisms of both neurotic and mature levels less frequently than normal adolescents did. Factor analysis revealed that, normal adolescents had higher scores on ego-expansive factor scales and behavior control factor scales thanadolescents with conduct disorder did. Conclusion : The results suggest adolescents with conduct disorder use mature and ego-expansive defense mechanisms less frequently than do normal adolescents.

• Journal of the Korean Ceramic Society
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• v.27 no.7
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• pp.869-876
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• 1990

Hexagonal boron nitride was synthesized from boron oxide and sodium amide in ammonia gas stream. The reaction mechanisms and characteristics of as synthesized boron nitride was investigated by means of TG, DTA, IR, XRD, SEM and PSA. The results are ; 1) hexagonal boron nitride was synthesized from reactions at temperatures above 40$0^{\circ}C$ 2) Sodium metaborate was present as by-product after reaction so that the reaction mechanism is reduced as follows : 2B2O3＋3NaNH2longrightarrowBN＋3NaBO2＋2NH3. 3) boron nitride obtained at the reaction temperature below 40$0^{\circ}C$ is found to have random layer strudcture but the structure transits to ordered layer structure rapidly with increasing reaction temperature, showing separation of (101) differaction line from (10)band in XRD pattern of the reaction product at 50$0^{\circ}C$.