• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.453-456
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• 2010

The structural and energetic preferences of thiacalix[4]biscrown-5 with and without alkali metal ions ($Na^+$, $K^+$, $Rb^+$, and $Cs^+$) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-$\pi$ interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1460-1464
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• 2014

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1995.05a
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• pp.31-34
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• 1995

The NO$_2$ gas-deteotion characteristics were investigated using the functional organic Langmuir-Blodgett(LB) files of Dilithium phthalocyanines(Li$_2$Pc). The optimum conditions for a film deposition were obtained through a study of $\pi$-A isotherms, and the deposited film status was confirmed by the ellipsometry measurements. A propel number of layers for the gas-detection was proved to be 9 layers from a measurement of a measurement of change in the electrical conductivities when the films were exposed to the 200 ppm of the NO$_2$ gases. A response time, recovery time, and reproducibility were also studied. A proper temperature which was able to activate gas interaction between NO$_2$ gases and Li$_2$Pc LB films was around 150$^{\circ}C$ judging from the electrical conductivities in a temperature range of 20 to 200$^{\circ}C$. It was found that at 150\ulcorner there are increments of electrical conductivities by 65 tines, 30 seconds of response time and 60 seconds of recovery tine when the filmswere exposed to the gasses.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2339-2344
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• 2011

Kinetic studies for the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide at 85.0 $^{\circ}C$. The Hammett and Br$\"{o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of the cross-interaction constant (${\rho}_{XZ}$) implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The magnitude of ${\rho}_{XZ}$ (= -0.35) for the strongly basic pyridines is greater than that (${\rho}_{XZ}$ = -0.15) for the weakly basic pyridines, indicating a change of the nucleophilic attacking direction from frontside for the strongly basic pyridines to backside for the weakly basic pyridines. The early transition state is proposed on the basis of the absence of positive deviations from both the Hammett and Br$\"{o}$nsted plots for the strong ${\pi}$-acceptor, X = 4-Ac, and small values of ${\rho}_{XZ}$ and ${\beta}_X$.

• Journal of the Korean Vacuum Society
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• v.3 no.3
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• pp.316-321
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• 1994

Rate of mixing of Cu particles to polyimide substrate at interfaces under different thermal treatments was analyzed by Rutherford Backscattering spectroscopy using 2.0 MeV He+ ions. T he mixing rate was a function of annealing temperature and time and was constant at afioxed temperature. The amount of mixing increased linearly with time and the mixing rate increased with temperature. The activation energy for interface mixing between Cu and polyimide was 2.6 kcal/mol. The X-ray studies showed the Cu(111) plane peak changed with annealing time at fixed temperature. The mixing of Cu to polyimide was explained with segmental motion of PI chain and with interaction between functional group of the chain and metal electron donor. The comparisons were made bewteen the mixing induced by ion irradiation and by thermal treatment. The various factors affecting the interface mixing are discussed.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.49 no.2
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• pp.87-91
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• 2000

Metal ion complex of poly(N-(2,4-imidazoly)ethyl)maleimide-alt-l-octadecene (IMO-O) polymer used to confirm the possibility of molecular device made by Langmuir-Blodgett(LB) method. Electrical properties of the metal ion complex LB film were investigated using Metal/Insulator/Metal(MIM) structure. In the surface pressure-area($\pi$-A) isotherm of IMI-O polymer, the surface pressure at collapse point has a difference due to the interaction between polymer and metal ions. And the complex between polymer and metal ions could be verified through the investigation by Raman spectroscopy. In the current-voltage(I-V) property, the conductivity change of IMO-O polymer complexes due to the kinds of metal of metal ions couldn't be observed. However, the limiting area of molecules was changed by the concentration of the metal ions and the conductivity was increased with the occupied molecular area.

• Macromolecular Research
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• v.14 no.1
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• pp.1-33
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• 2006

Polyimides (PIs) exhibit excellent thermal stability, mechanical, dielectric, and chemical resistance properties due to their heterocyclic imide rings and aromatic rings on the backbone. Due to these advantageous properties, PIs have found diverse applications in industry. Most PIs are insoluble because of the nature of the high chemical resistance. Thus, they are generally used as a soluble precursor polymer, which forms complexes with solvent molecules, and then finally converts to the corresponding polyimides via imidization reaction. This complexation with solvent has caused severe difficulty in the characterization of the precursor polymers. However, significant progress has recently been made on the detailed characterization of PI precursors and their imidization reaction. On the other hand, much research effort has been exerted to reduce the dielectric constant of PIs, as demanded in the microelectronics industry, through chemical modifications, as well as to develop high performance, light-emitting PIs and liquid crystal (LC) alignment layer PIs with both rubbing and rubbing-free processibility, which are desired in the flat-panel display industry. This article reviews this recent research progresses in characterizing PIs and their precursors and in developing low dielectric constant, light-emitting, and LC alignment layer PIs.

• Bulletin of the Korean Chemical Society
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• v.24 no.3
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• pp.325-333
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• 2003

An analysis of the electronic structure and bonding in the ternary silicide YNiSi₃is made, using extended Huckel tight-binding calculations. The YNiSi₃structure consists of Ni-capped Si₂dimer layers and Si zigzag chains. Significant bonding interactions are present between the silicon atoms in the structure. The oxidation state formalism of $(Y^{3+})(Ni^0)(Si^3)^{3-}$ for YNiSi₃constitutes a good starting point to describe its electronic structure. Si atoms receive electrons from the most electropositive Y in YNiSi₃, and Ni 3d and Si 3p states dominate below the Fermi level. There is an interesting electron balance between the two Si and Ni sublattices. Since the ${\pi}^*$ orbitals in the Si chain and the Ni d and s block levels are almost completely occupied, the charge balance for YNiSi₃can be rewritten as $(Y^{3+})(Ni^{2-})(Si^{2-})(Si-Si)^+$, making the Si₂layers oxidized. These results suggest that the Si zigzag chain contains single bonds and the Si₂double layer possesses single bonds within a dimer with a partial double bond character. Strong Si-Si and Ni-Si bonding interactions are important for giving stability to the structure, while essentially no metal-metal bonding exists at all. The 2D metallic behavior of this compound is due to the Si-Si interaction leading to dispersion of the several Si₂π bands crossing the Fermi level in the plane perpendicular to the crystallographic b axis.

• Macromolecular Research
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• v.17 no.2
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• pp.104-109
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• 2009

Solid-state facilitated, olefin transport membranes were prepared by complexation of poly(styrene-b-iso-prene-b-styrene) (SIS) block copolymer and silver salt. Facilitated olefin transport was not observed up to a silver mole fraction of 0.14, representing a threshold concentration, above which transport increased almost linearly with increasing silver salt concentration. This was because firstly the silver ions were selectively coordinated with the C=C bonds of PI blocks up to a silver mole fraction of 0.20, and secondly the coordinative interaction of the silver ions with the aliphatic C=C bond was stronger than that with the aromatic C=C bond, as confirmed by FT-Raman spectroscopy. Small angle X-ray scattering (SAXS) analysis showed that the cylindrical morphology of the neat SIS block copolymer was changed to a disordered structure at low silver concentrations ($0.01{\sim}0.02$). However, at intermediate silver concentrations ($0.15{\sim}0.20$), disordered-ordered structural changes occurred and finally returned to a disordered structure again at higher silver concentrations (>0.33). These results demonstrated that the facilitated olefin transport of SIS/silver salt complex membrancs was significantly affected by their coordinative interactions and nano-structural morphology.

• Structural Engineering and Mechanics
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• v.14 no.2
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• pp.151-170
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• 2002

Moving force identification is a very important inverse problem in structural dynamics. Most of the identification methods are eventually converted to a linear algebraic equation set. Different ways to solve the equation set may lead to solutions with completely different levels of accuracy. Based on the measured bending moment responses of the bridge made in laboratory, this paper presented the time domain method (TDM) and frequency-time domain method (FTDM) for identifying the two moving wheel loads of a vehicle moving across a bridge. Directly calculating pseudo-inverse (PI) matrix and using the singular value decomposition (SVD) technique are adopted as means for solving the over-determined system equation in the TDM and FTDM. The effects of bridge and vehicle parameters on the TDM and FTDM are also investigated. Assessment results show that the SVD technique can effectively improve identification accuracy when using the TDM and FTDM, particularly in the case of the FTDM. This improved accuracy makes the TDM and FTDM more feasible and acceptable as methods for moving force identification.