• Journal of Photoscience
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• v.6 no.3
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• pp.103-108
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• 1999

We present recent results on ablation mechanism, single-pulse laser micropatterning , pulsed-laser deposition(PLD) and particulates formation accompanying laser ablation, with special emplasis on polymers, in particular polymide, (PI), and polytetrafluoroethylene, (PTFE). Ablation of polymers is described on the basis of photothermal bond breaking within the bulk material. Here, we assume a first order chemical reaction, which can be described by an Arrhenius law. Ablation starts when the density of broken bonds at the surface reaches a certain critical value. Single-pulse laser ablation of polyimide shows a clear-length dependence of the threshold fluence. This experimental result strongly supports a thermal ablation model. We discuss the various possibilities and drawbacks of PLD and describe the morphology, physical properties and applications of PTFE films.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.18-23
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• 1997

Data from structure/activity studies in vir gene induction system have led to evaluate the working hypothesis of interaction between phenolic inducers and phenol binding proteins. The primary specificity in the association of a phenolic inducer with its receptor in our system is hypothesized to be the hydrogen bonding interactions through the ortho methoxy substituents as well as the proton transfer between the inducer and the binding protein. In this paper the proposed working model for phenol-mediating signal transduction was evaluated in several ways. The importance of the general acid-base catalysis was first addressed by the presence of an acidic residue and a basic residue in the phenol binding protein. Series of compounds were tested for vir gene expression activity to confirm the generation of a strong nucleophile by an acidic residue and an involvement of a basic residue as a proton acceptor. An attempt was made to correlate the pKa values of the phenolic compounds with vir gene induction activities as inducers to further support the proposed proton transfer mechanism. Finally, it was also observed that the regioselectively attached methoxy group on phenol compounds is required as the proper hydrogen bond acceptor.

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Bulletin of the Korean Chemical Society
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• v.10 no.5
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• pp.443-447
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• 1989

The mechanism on the oxidative addition reaction of $(TBA)_2\;Pt(CN)_4$ with $Cl_2$ has been studied by means of extended Huckel calculations. Among two possible mechanisms, computational calculations demonstrated that the linear approach of $Cl_2$ to a $Pt(CN)_4$ moiety is more favourable than three-centered transition state. From our calculations, the most stable process is that a $Pt(CN)_4$ moiety interacts with $Cl_2$ in the linear transition state and the cleavage of Cl-Cl bond in a coordinated halogen occurred spontaneously, giving rise to a trans product by back-attacking a $Pt(CN)_4Cl$ moiety by Cl. The process consists of the comparison in the stability of each intermediate with use of bonding and potential energy.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1063-1068
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• 1998

The nature of F electronic excitation energy transfer to OH- vibrational levels in KCl crystals is the exchange interaction, although the transfer process exhibits three temporally distinguishable components depending on the distance between excited F center and OH-. The critical distance as well as rate of the major energy transfer process in randomly distributed samples increases rapidly as OH- librational motions become active with temperature rise. The excited state character introduced into the OH- ground electronic state by perturbation is essential for the exchange interaction. The perturbation is brought about by the expanded electron cloud of excited F center for OH- associated to F center, whereas by librations and lattice vibrations perpendicular to the bond axis for isolated OH- . F excitation quenching efficiency by OH- is dependent on the variation of the critical distance rather than the rate as the rate is much faster than the normal F bleach recovery rate.

• Bulletin of the Korean Chemical Society
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• v.16 no.12
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• pp.1203-1208
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• 1995

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

• Bulletin of the Korean Chemical Society
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• v.7 no.4
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• pp.279-282
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• 1986

The MNDO calculations were performed in order to investigate the gas-phase reaction mechanism of 2-propene-1-al oxide, as a model compound of dypnone oxide(1,3-diphenyl-2-butene-1-one oxide) with the chloride ion. Optimized geometries and heats of formation for two probable concerted pathways, CHO and H migration, were determined and their activation energies were obtained. MO results show that although the formyl migration is thermodynamically more favorable than the hydride migration, the latter kinetically predominates over the formyl migration, which is contrary to the established migrating preferences. It is concluded that the hydride migratory propensity is catalyzed by the chloride ion by reducing the capability of the carbonyl ${\pi}$ bond to participate in the migration.

• Proceedings of the PSK Conference
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• 2003.04a
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• pp.241.2-241.2
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• 2003

We report the synthesis of key intermediates for the development novel flavonoid derivatives with potential antiinflammatory activity and propose a mechanism of the one-pot reaction. The various amines (1) for this work were commercially available. Secondary amines (2) were formed by nucleophilic attraction using ethyl benzoylacetate. The C-N bond formation proceeded at refluxing in toluene with catalytic amount of p-toluenesulfonic acid and a removal of water was important in this reaction. (omitted)

• Proceedings of the PSK Conference
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• 2003.10b
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• pp.183.2-183.2
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• 2003

We report the synthesis of 3,4-dihydro-2-oxo-4-quinolines 5a-e for the development novel flavonoid derivatives with potential antiinflammatory activity and propose a mechanism of the one-pot reaction. The various amines (la-e) for this work were commercially available. We isolated that ester (2a-e) were formed by nucleophilic attraction using ethyl benzoylacetate. The C-N bond formation proceeded at refluxing in toluene with catalytic amount of p-toluenesulfonic acid and a removal of water and ethanol was important in this reaction. (omitted)

• Proceedings of the PSK Conference
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• 2002.10a
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• pp.231.1-231.1
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• 2002

The anaerobic pathway for unsaturated fatty acid biosynthesis was established in the 1960s in Escherichia coli. The double bond is introduced into the growing acyl chain by FabA., an enzyme capable of both the dehydration of ${\beta}$-hydroxdecanoyl-［acyl carrier protein］ (ACP) to trans-2-decenoyl-ACP. and the isomerization of trans-2 to cis-3-decenoyl-ACP. However. there are a number of anaerobic bacteria whose genomes do not contain a fabA homolog, but these organisms nonetheless produce unsaturated fatty acids. (omitted)